Adrien Soupart

Fabienne Alary

Jean-Louis Heully

Paul I P Elliott

Isabelle M Dixon
email: isabelle.dixon@irsamc.ups-tlse.fr

Jean-Pierre Sauvage

Recent progress in ligand photorelease reaction mechanisms: Theoretical insights focusing on Ru(II) 3MC states

Keywords: photoreactivity mechanisms, inorganic photochemistry, theoretical chemistry, DFT, potential energy surfaces, metal-centered excited states

Introduction

The interplay between the metal-to-ligand charge transfer (MLCT) and metal-centred (MC) excited states of Ru(II) complexes is at the heart of modern inorganic photochemistry. These two states are the key protagonists towards both the photophysical (photoluminescence, photoinduced electron or energy transfer) and photochemical (photoisomerization, photorelease) properties of this family of compounds, the balance of which is crucial in terms of potential applications. Photostability is indeed a critical issue for photophysical applications (e.g. photosensitizing for photodynamic therapy [START_REF] Mari | Combination of Ru(II) complexes and light: new frontiers in cancer therapy[END_REF][2][3] [START_REF] Liu | Harnessing ruthenium(II) as photodynamic agents: Encouraging advances in cancer therapy[END_REF], photocatalysis [START_REF] Prier | Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis[END_REF][6] [7], sensing and imaging [START_REF] Gill | A ruthenium(II) polypyridyl complex for direct imaging of DNA structure in living cells[END_REF], or solar energy conversion [START_REF] Pashaei | Influence of Ancillary Ligands in Dye-Sensitized Solar Cells[END_REF]), while the opposite is sought for photochemical applications [START_REF] Daniel | Chemical bonding alteration upon electronic excitation in transition metal complexes[END_REF] such as synthetic purposes [START_REF] Wallace | A Simple Photochemical Synthesis of Some Bis(bipyridyl)ruthenium(II) Complexes[END_REF] [START_REF] Durham | Synthetic Applications of Photosubstitution Reactions of Poly(pyridyl) Complexes of Ruthenium(II)[END_REF][13] [START_REF] Hecker | Evidence for Dissociative Photosubstitution Reactions of [Ru(trpy)(bpy)(NCCH 3 )] 2+ . Crystal and Molecular Structure of [Ru(trpy)(bpy)(py)](PF 6 ) 2 .(CH 3 ) 2 CO[END_REF], photorelease of biologically active moieties [START_REF] Ford | Metal complex strategies for photo-uncaging the small molecule bioregulators nitric oxide and carbon monoxide[END_REF][16] [START_REF] Li | Ru(II) polypyridyl complexes as photocages for bioactive compounds containing nitriles and aromatic heterocycles[END_REF][18] [START_REF] Bonnet | Why develop photoactivated chemotherapy?[END_REF] or phototriggered molecular machines [START_REF] Colasson | Light-driven molecular machines based on ruthenium(II) polypyridine complexes: Strategies and recent advances[END_REF].

Several experimental and theoretical studies have contributed to providing valuable information in terms of microscopic mechanistic details relevant to ligand photorelease from Ru(II) complexes [21][22][23] [START_REF] Liu | Ultrafast Ligand Exchange: Detection of a Pentacoordinate Ru(II) Intermediate and Product Formation[END_REF][25] [START_REF] Salassa | Photo-Induced Pyridine Substitution in cis-[Ru(bpy) 2 (py) 2 Cl 2 : A Snapshot by Time-Resolved X-ray Solution Scattering[END_REF][27] [START_REF] Ding | Excited-State Proton Transfer Controls Irreversibility of Photoisomerization in Mononuclear Ruthenium(II) Monoaquo Complexes: A DFT Study[END_REF][29] [START_REF] Camilo | Photosolvolysis of cis-[Ru(αdiimine) 2 (4-aminopyridine) 2 ] 2+ Complexes: Photophysical, Spectroscopic, and Density Functional Theory Analysis[END_REF][31] [START_REF] Word | Photoacoustic calorimetry study of ligand photorelease from the Ru(II)bis(2,2′-bipyridine)(6,6′-dimethyl-2,2′-bipyridine) complex in aqueous solution[END_REF][33] [START_REF] Scattergood | Photochemistry of [Ru(pytz)(btz) 2 ] 2+ and Characterization of a κ 1 -btz Ligand-Loss Intermediate[END_REF][35] [START_REF] Nisbett | DFT Investigation of Ligand Photodissociation in [Ru(II)(tpy)(bpy)(py)] 2+ and [Ru(II)(tpy)(Me 2 bpy)(py)] 2+ Complexes[END_REF].

However they also highlight the intrinsic complexity of studying multistep light-induced reactions under experimental conditions that affect the reaction course, particularly solvent [START_REF] Orr-Ewing | Taking the plunge: chemical reaction dynamics in liquids[END_REF]. Major gaps remain in this field, and this review aims at summarizing our recent contributions via joint experimental-theoretical studies. Our knowledge of the topology of the ground potential energy surface ( 1 PES) and of the lowest triplet potential energy surface ( 3 PES) has gradually improved to a point where we can now build up and propose multistep photorelease reaction mechanisms along with the microscopic description of the states involved.

Context and theoretical methods: 3 MC-mediated excited state deactivation in [Ru(bpy) 3 ] 2+ and [Ru(tpy) 2 ] 2+ as an illustration

Thermal ligand exchange is a key contributor to the function of metalloenzymes in Nature [START_REF] Blomberg | Quantum Chemical Studies of Mechanisms for Metalloenzymes[END_REF]. Photochemical ligand release, on the other hand, is specific to thermally stable compounds and can be triggered at will with efficient time, energy and space selectivities.

The establishment of photoreactivity mechanisms implies that one has a good knowledge of all the different excited states that are (susceptible to be) populated following light irradiation.

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

In the case of Ru(II) complexes such as those described here, the available ground and excited states and the interconversions between them are commonly described using a Jablonksi diagram (Figure 1a). For these complexes, the presence of π-accepting ligands such as polypyridines ensures the presence of low-lying 1 MLCT states that will provide lightabsorption capabilities in the visible region of the electromagnetic spectrum. Following fast and quantitative intersystem crossing [START_REF] Marian | Spin-orbit coupling and intersystem crossing in molecules: Spin-orbit coupling[END_REF][40], 3 MLCT states are populated within in a few hundreds of fs [START_REF] Damrauer | Femtosecond Dynamics of Excited-State Evolution in [Ru(bpy) 3 ] 2+[END_REF]. 3 MLCT states are thus the first ones to be scrutinized, the radiative deactivation of which can be modeled using a variety of theoretical methods. Some of them take into account the spin orbit coupling (SOC) between the lowest 3 MLCT state and the ground state, allowing electronic states of different spin multiplicity to couple. For [Ru(bpy) 3 ] 2+ (bpy = 2,2'-bipyridine) we have shown that the emissive MLCT state is predominantly triplet in character, to such an extent that excited state energies with or without SOC are similar within the accuracy of the method [START_REF] Heully | Spin-orbit effects on the photophysical properties of Ru(bpy) 3 2+[END_REF]. Another method takes into account the vibrational coupling between the emitting state and the ground state and is a powerful tool for modeling experimental emission band envelopes. Indeed, theoretical Vibrationally Resolved Electronic Spectroscopy (VRES) [43][44] is in excellent agreement with the experimental emission data for [Ru(bpy) 3 ] 2+ [START_REF] Soupart | DFT rationalization of the roomtemperature luminescence properties of Ru(bpy) 3 2+ and Ru(tpy) 2 2+ : 3 MLCT-3 MC minimum energy path from NEB calculations and emission spectra from VRES calculations[END_REF], and also allows a very subtle analysis of the vibronic fine structure (see ref [START_REF] Farouil | Revisiting the Vibrational and Optical Properties of P3HT: A Combined Experimental and Theoretical Study[END_REF] for an example in absorption spectroscopy), the interpretation of which being particularly challenging in the absence of a theoretical model. 3 MLCT states can also deactivate nonradiatively, either by direct surface crossing with the ground state (e.g. for Ru(II) cyclometallated complexes [START_REF] Kreitner | Excited state decay of cyclometalated polypyridine ruthenium complexes: insight from theory and experiment[END_REF]) or through heat transfer to their environment [37][48]. They may also undergo internal conversion to 3 MC states, the latter being held responsible both for efficient nonradiative deactivation and chemical decomposition. As 3 MC states are associated with the population of an antibonding dσ* orbital, significant Ru-N bond elongations occur [START_REF] Alary | Is the 3 MLCT the Only Photoreactive State of Polypyridyl Complexes?[END_REF]. The simple Jablonski diagram does not take into account such structural deformations and therefore only offers a partial representation of the system. A more global picture is brought by a potential energy surface description, in which the structural deformations that characterise 3 MC states can be regarded as the reaction coordinate (Figure 1b).

As the archetypical [Ru(bpy) 3 ] 2+ (Figure 2) is rather photostable, and [Ru(tpy) 2 ] 2+

(tpy = 2,2':6',2"-terpyridine) is truly [START_REF] Bonnet | Ruthenium-based light-driven molecular machine prototypes: synthesis and properties[END_REF], we will first focus on the nonradiative deactivation of their 3 MC states. To do so, the minimum energy crossing point ( 3/1 MECP, Figure 1b) between the singlet and the triplet PES should be optimized [51][52]. The similarities, both in structure and energy, to the corresponding 3 MC state and the topology of the crossing itself Regarding the internal MLCT-MC conversion process itself, consisting in an electron transfer from a ligand-based π* orbital to a metal-based dσ* orbital, this can be probed theoretically by optimizing the transition state that connects these two minima [START_REF] Göttle | Adiabatic Versus Nonadiabatic Photoisomerization in Photochromic Ruthenium Sulfoxide Complexes: A Mechanistic Picture from Density Functional Theory Calculations[END_REF][56] [START_REF] Breivogel | Excited State Tuning of Bis(tridentate) Ruthenium(II) Polypyridine Chromophores by Push-Pull Effects and Bite Angle Optimization: A Comprehensive Experimental and Theoretical Study[END_REF] or, in a more

N N N N N N N N N N N N Ru Ru 2+ 2+
Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184 approximate fashion, by running a relaxed surface scan along a user-defined reaction coordinate [START_REF] Salassa | Mechanism of Ligand Photodissociation in Photoactivable [Ru(bpy) 2 L 2 ] 2+ Complexes: A Density Functional Theory Study[END_REF][58] [START_REF] Sun | Ultrafast transient IR spectroscopy and DFT calculations of ruthenium(II) polypyridyl complexes[END_REF], in this case Ru-N bond elongation along one N-Ru-N axis.

Alternatively, the minimum energy path (MEP) can be computed using a method such as the Nudged Elastic Band (NEB) [START_REF] Jonsson | Nudged Elastic Band Method for Finding Minimum Energy Paths of Transitions[END_REF] [START_REF] Henkelman | Methods for Finding Saddle Points and Minimum Energy Paths[END_REF], which is the one we have been using for several years.

The NEB method starts from an initial path connecting two geometries. Relaxation of this initial path leads to the MEP through path gradient and tangent information. This method displays the great advantage over a relaxed surface scan that the reaction coordinate is userindependent, being initially mathematically defined (IDPP method in our case [START_REF] Smidstrup | Improved initial guess for minimum energy path calculations[END_REF]) and, along the converged path, being the actual physical reaction coordinate. The highest energy point along the MEP also provides an excellent guess for transition state optimization. Until now the NEB method has scarcely been used in molecular chemistry but it has proved very powerful in our hands. Its implementation within more and more quantum chemistry codes certainly promises a bright future to it.

To illustrate and validate the use of these methods in the context of inorganic photochemistry, we have confronted the available experimental data with our computed data for the archetype complexes [Ru(bpy) 3 ] 2+ and [Ru(tpy) 2 ] 2+ (Figure 2). [Ru(bpy) 3 ] 2+ (as well as 2,2'-bipyrazine and 1,4,5,8-tetraazaphenanthrene complexes) were initially studied in vacuum under symmetry constraints for obvious matters of computational resources [START_REF] Alary | Is the 3 MLCT the Only Photoreactive State of Polypyridyl Complexes?[END_REF][63] [START_REF] Heully | Spin-orbit effects on the photophysical properties of Ru(bpy) 3 2+[END_REF]. Nowadays these technical restrictions no longer apply on such molecular systems, which is why the states discussed in this review were optimized in implicit solvent without symmetry. In line with the occupation of a dσ* orbital in the 3 MC state, major bond elongations are observed in such structures: two elongations in the case of the tris(bidentate) complex, four elongations in the case of the bis(terdentate) one (Figure 3).

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

Figure 3. 3 MC state of [Ru(bpy) 3 ] 2+ and [Ru(tpy) 2 ] 2+ with their SOMO+1 and the corresponding key Ru-N elongations (distances in Å).

The optimization of the 3 MLCT and 3 MC minima provides us with Jablonski diagrams for the two complexes that display similar 3 MLCT energies (46-47 kcal/mol with respect to the ground state) and similar 3 MLCT-3 MC energy gaps (3-4 kcal/mol) [START_REF] Soupart | DFT rationalization of the roomtemperature luminescence properties of Ru(bpy) 3 2+ and Ru(tpy) 2 2+ : 3 MLCT-3 MC minimum energy path from NEB calculations and emission spectra from VRES calculations[END_REF]. Rationalization of the room temperature luminescence of [Ru(bpy) 3 ] 2+ versus the nonluminescence of [Ru(tpy) 2 ] 2+ thus requires us to go beyond this Jablonski diagram. Computation of the minimum energy path for the 3 MLCT-3 MC conversion gives an activation energy of 9 kcal/mol for bpy but only 4 kcal/mol for tpy, in line with a more efficient population of the 3 MC state in the tpy case. In addition, these activation energies compare remarkably well with those obtained from variable temperature luminescence lifetimes measurements (11 kcal/mol for [Ru(bpy) 3 ] 2+ [START_REF] Caspar | Photochemistry of Ru(bpy) 3 2+ . Solvent Effects[END_REF] and 5 kcal/mol for [Ru(tpy) 2 ] 2+ [START_REF] Amini | The triplet excited state of ruthenium(II) bis(2,2′:6′,2″-terpyridine): Comparison between experiment and theory[END_REF]). Finally, optimization of the 3/1 MECPs shows that the 3 MC-3/1 MECP energy gap is 6 kcal/mol for bpy but only 1 kcal/mol for tpy, in line with the much smaller geometrical distortions observed between the 3 MC state and the 3/1 MECP for tpy. Nonradiative deactivation is thus expected to be much more favourable and efficient for [Ru(tpy) 2 ] 2+ than for [Ru(bpy) 3 ] 2+ . Combining minima and MECP optimization with the computation of the minimum energy path for internal conversion on the 3 PES (Scheme 1) has overall provided us with the rationalization of the photophysical properties of the two major archetypes of Ru(II) photochemistry [START_REF] Soupart | DFT rationalization of the roomtemperature luminescence properties of Ru(bpy) 3 2+ and Ru(tpy) 2 2+ : 3 MLCT-3 MC minimum energy path from NEB calculations and emission spectra from VRES calculations[END_REF].

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

Scheme 1: Potential energy curves computed for [Ru(bpy) 3 ] 2+ (left) and [Ru(tpy) 2 ] 2+ (right) [45].

Having validated the methods and having gained a significant experience of their use on coordination compounds in their ground and excited states, we have embarked on applying them to more challenging projects involving photoinduced ligand release. This has enabled us to develop strategies for their systematic use to map the topology of both the singlet and triplet PES as a highly convenient alternative to relaxed surface scan approaches.

Photorelease of a monodentate ligand

Photoactivated chemotherapy involves the light-induced breaking of a chemical bond that releases at least one biologically active fragment. The goal of realising effective and applicable photoactivated chemotherapeutic complexes has therefore driven significant experimental efforts for the investigation of ligand release photochemistry. In the course of their studies on the photorelease of thioether ligands from Ru(II) complexes, Bonnet et al.

obtained strikingly different photosubstitution yields (φ(photosub.)) depending on the bidentate ligand that was bound to the metal, ranging from 2% to an impressive 30% (Scheme 2) [START_REF] Bahreman | Spontaneous Formation in the Dark, and Visible Light-Induced Cleavage, of a Ru-S Bond in Water: A Thermodynamic and Kinetic Study[END_REF]. The method by which the photosubstitution yields were estimated is reported in the original publication [START_REF] Bahreman | Spontaneous Formation in the Dark, and Visible Light-Induced Cleavage, of a Ru-S Bond in Water: A Thermodynamic and Kinetic Study[END_REF]. Theoretical studies were subsequently undertaken to rationalize this behaviour.

Scheme 2: Monodentate thioether photosubstitution yields φ(photosub.) [66].

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

An intuitive approximation of the reaction coordinate involved in the release of a monodentate ligand is the distance between the metal and the initally bound/eventually unbound atom. From the practical point of view of a theoretician, this distance is a natural parameter to be scanned in a relaxed surface scan [START_REF] Salassa | Mechanism of Ligand Photodissociation in Photoactivable [Ru(bpy) 2 L 2 ] 2+ Complexes: A Density Functional Theory Study[END_REF] [START_REF] Camilo | Photosolvolysis of cis-[Ru(αdiimine) 2 (4-aminopyridine) 2 ] 2+ Complexes: Photophysical, Spectroscopic, and Density Functional Theory Analysis[END_REF][33] [START_REF] Nisbett | DFT Investigation of Ligand Photodissociation in [Ru(II)(tpy)(bpy)(py)] 2+ and [Ru(II)(tpy)(Me 2 bpy)(py)] 2+ Complexes[END_REF]. We have performed geometry optimizations followed by NEB minimum energy path calculations and transition state optimizations on the four complexes shown in Scheme 2. These calculations point to the fact that two local minima could be located in the 3 MC region, both displaying major elongations towards the thioether ligand but to various degrees. Indeed, for dcbpy and biq, which display intermediate photosubstitution yields, a 3 MC state with a closely associated thioether ligand (Ru-S≈3 Å) was obtained, called 3 MC hexa , as well as a 3 MC state with a significantly extended Ru-S distance of ~4 Å, called 3 MC penta . The 3 MC hexa -3 MC penta internal conversion process is slightly downhill and its activation energy is minimal, less than 3 kcal/mol. For bpy, which displays the lowest ϕ(photosub.), only 3 MC hexa was obtained. On the contrary, for dmbpy, which displays the highest ϕ(photosub.), only 3 MC penta could be located. This combination of factors has led us to propose the following mechanistic hypothesis: 3 MC hexa with a shorter Ru-S distance would be prone to geminate recombination through the associated 3/1 MECP that leads the system back to the reactant ground state; on the other hand, 3 MC penta with a far longer Ru-S distance would be prone to ligand dissociation, following diffusion of its weakly bound thioether ligand, which in turn would lead towards the photoproduct through solvent trapping (Scheme 3) [START_REF] Göttle | Pivotal Role of a Pentacoordinate 3 MC State on the Photocleavage Efficiency of a Thioether Ligand in Ruthenium(II) Complexes: A Theoretical Mechanistic Study[END_REF]. This therefore explains the highly differing photochemical ligand ejection efficiencies displayed by the bpy and dmbpy complexes. Further, the intermediate efficiencies of the dcbpy and biq complexes can then be rationalised by the population of 3 MC penta necessitating transient population of 3 MC hexa , with its associated potential leak towards reactant.

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

Scheme 3: Triplet free energy profiles for the bpy (red), dcbpy (green), biq (blue) and dmbpy (black) complexes in water at 298 K ( 3 MLCT states aligned for comparison purposes). The preferential roles assigned to 3 MC hexa (geminate recombination towards starting material, orange arrow) and 3 MC penta (evolution towards photoproduct, purple arrow) are schematized through crossings with the relevant singlet PES. Illustration with the biq ligand showing the chemical structure and Ru-S distance in the 3 MC states proposed to play two

distinct roles [START_REF] Göttle | Pivotal Role of a Pentacoordinate 3 MC State on the Photocleavage Efficiency of a Thioether Ligand in Ruthenium(II) Complexes: A Theoretical Mechanistic Study[END_REF].

Photorelease of a bidentate ligand

Although the most common photolabilized ligands are monodentate ( [START_REF] Li | Ru(II) polypyridyl complexes as photocages for bioactive compounds containing nitriles and aromatic heterocycles[END_REF][18] and references therein), there are a few examples where bidentate ligands such as diimines [START_REF] Howerton | Strained Ruthenium Complexes Are Potent Light-Activated Anticancer Agents[END_REF][69][70] [START_REF] Li | Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex[END_REF] or aminoacids [START_REF] Cuello-Garibo | Influence of the Steric Bulk and Solvent on the Photoreactivity of Ruthenium Polypyridyl Coord[END_REF] have been photoreleased, or 'photouncaged' in the jargon, from Ru(II) complexes, to reveal their biological activity. Alternatively the photoejection of bidentate ligands has been used as an efficient trigger for molecular machines [START_REF] Baranoff | A photochromic system based on photochemical or thermal chelate exchange on Ru(phen)2L2+ (L = diimine or dinitrile ligand)[END_REF] [START_REF] Laemmel | Macrocyclic Complexes of [Ru(N-N) 2 ] 2+ Units [N-N= 1, 10 Phenanthroline or 4-(p-Anisyl)-1, 10-Phenanthroline]: Synthesis and Photochemical Expulsion Studies[END_REF][75] [START_REF] Collin | Light-Driven Expulsion of the Sterically Hindering Ligand L in Tris-diimine Ruthenium(II) Complexes of the Ru(phen) 2 (L) 2+ Family: A Pronounced Ring Effect[END_REF] [START_REF] Bonnet | Ruthenium-based light-driven molecular machine prototypes: synthesis and properties[END_REF].

Experimental work in the Elliott group has largely focussed on the photophysical properties of complexes of 1,2,3-triazole-based ligands as analogues for more conventional polypyridyl ligand systems [START_REF] Scattergood | An unexpected journey from highly tunable phosphorescence to novel photochemistry of 1,2,3-triazole-based complexes[END_REF]. Whilst these ligand systems have proved enormously versatile the preparation of complexes for luminescent applications [START_REF] Scattergood | Photophysics and photochemistry of 1,2,3-triazole-based complexes[END_REF], they have also offered significant and unique insights into photoreactive excited state processes. During the course of our investigations in this field, we designed a series of complexes containing various proportions of bpy and btz ligands (btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl) [START_REF] Welby | Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes: fundamental switching of the nature of S 1 and T 1 states from MLCT to MC[END_REF] with the aim of gradually narrowing the energy gap from the bpy-localised 3 MLCT state to the potentially dissociative 3 MC states in order to favour ligand photorelease with increasing btz content [START_REF] Scattergood | An unexpected journey from highly tunable phosphorescence to novel photochemistry of 1,2,3-triazole-based complexes[END_REF].

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184 Indeed, both the heteroleptic complexes [Ru(bpy) 2 (btz)] 2+ and [Ru(bpy)(btz) 2 ] 2+ prove to be photochemically reactive with release of a btz ligand in donor solvents [START_REF] Welby | Unambiguous Characterization of a Photoreactive Ligand-Loss Intermediate[END_REF] [START_REF] Welby | Photochemical ligand ejection from non-sterically promoted Ru(II)bis(diimine) 4,4′-bi-1,2,3triazolyl complexes[END_REF]. Whilst [Ru(bpy) 2 (btz)] 2+ releases btz in acetonitrile to form cis-[Ru(bpy) 2 (NCMe) 2 ] 2+ in a similar manner to that observed for other Ru(II) complexes (e.g. [Ru(bpy) 2 (dmbpy)] 2+ [START_REF] Howerton | Strained Ruthenium Complexes Are Potent Light-Activated Anticancer Agents[END_REF]), the alternative heteroleptic complex [Ru(bpy)(btz) 2 ] 2+ displays highly novel photochemical behaviour; during the process of release of one of the btz ligands the retained bidentate ligands undergo rearrangement such that they become coplanar in the photoproduct trans-[Ru(bpy)(btz)(NCMe) 2 ] 2+ (Scheme 4). Significantly, this proceeds with observation of an intermediate photoproduct in which one btz ligand is coordinated in the monodentate fashion and which shows a high degree of stability. Remarkably, this allowed us to crystallize and structurally characterise the intermediate photoproduct (Figure 4) [START_REF] Welby | Unambiguous Characterization of a Photoreactive Ligand-Loss Intermediate[END_REF]. [START_REF] Welby | Unambiguous Characterization of a Photoreactive Ligand-Loss Intermediate[END_REF] From a mechanistic point of view, the isolation and structural characterization of a complex bearing a monodentate btz ligand trans to the incoming MeCN ligand unambiguously demonstrated the existence of κ 1 half-bound bidentate ligand complexes that had long been postulated in solution for this and other systems leading to cis photoproducts [START_REF] Van Houten | Photochemistry of Tris(2,2'-bipyridyl)ruthenium(II) in Aqueous Solution[END_REF][83] [START_REF] Tachiyashiki | Identification of an Intermediate of the Photosubstitution of a Ruthenium(II) Diimine Complex With a Monodentate Chelating Ligand: 1 H NMR and HPLC Evidence[END_REF][85].

Scheme 4. Two-step photochemical reactivity of [Ru(bpy)(btz) 2 ] 2+ in acetonitrile, involving two successive onephoton absorptions .

Figure 4: ORTEP diagrams of the intermediate photoproduct trans-[Ru(bpy)(κ 2 -btz)(κ 1 -btz)(NCMe)] 2+ (left) and of the final photoproduct trans-[Ru(bpy)(btz)(NCMe) 2 ] 2+ (right) (phenyl groups of the benzyl substituents of the triazole rings have been removed for clarity; H atoms and counterions not shown)

We then had in hand the experimental evidence of a stepwise process requiring two separate one-photon absorptions, taking place under continuous irradiation in acetonitrile, the second step requiring much longer irradiation times than the first one [START_REF] Welby | Photochemistry of Ru(II) 4,4′-Bi-1,2,3-triazolyl (btz) Complexes: Crystallographic Characterization of the Photoreactive Ligand-Loss Intermediate trans-[Ru(bpy)(κ 2 -btz)(κ 1 -btz)(NCMe)] 2+[END_REF]. Theoretical mechanistic investigations initially involved the determination of 3 MLCT and axially elongated 3 MC minima (inspired by the geometric parameters for the 3 MC state described earlier for [Ru(bpy) 3 ] 2+ ) and relaxed surface scans between these states (although the definition of the reaction coordinate is not as trivial as with a monodentate ligand). These scans allowed us to identify a previously unreported 3 MC local minimum repelling a single bidentate ligand through the elongation of two cis Ru-N bonds, which thus seemed a much better candidate for btz release than classical MC states displaying two trans elongations towards two different ligands (Figure 5). In addition this new type of 3 MC state displays a flattened geometry in relation to the widening of the angle between the two unrepelled ligands and thus approaching the coplanar arrangement observed in the photoproducts [START_REF] Dixon | Theoretical illumination of highly original photoreactive 3 MC states and the mechanism of the photochemistry of Ru(II) tris(bidentate) complexes[END_REF].

Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

Figure 5: Examples of classical (trans-elongated, A/B) and flattened (cis-elongated, F) 3 MC minima with remarkable distances along the most elongated bonds (a+d, b+c or a+b) and angles. Electronic energies with respect to that of the ground state [87].

Once flattened cis-elongated 3 MC(F) states are populated, and given the fact that we know, from the crystal structure of the intermediate photoproduct, that the two unrepelled ligands will eventually become coplanar, we were able to build a guess geometry and subsequently optimize another local 3 MC minimum bearing this approximate coplanarity, shown as 3 MC(P) on Figure 6. Here the 'P' stands for pentacoordinate as one of the Ru-N distances has significantly increased to 3.2 Å and the ligand can therefore be considered to have formally undergone dechelation.

Minimum energy crossing points were located for the hexacoordinate 3 MC(A/B/F) states which were found to connect to the 1 PES of the reactant complex in a similar manner to the 3 MC state of [Ru(bpy) 3 ] 2+ and the 3 MC hexa states of the [Ru(tpy)(diimine)(thioether)] 2+ series (vide supra). However, in the neighbourhood of 3 MC(P) state lies a crucial minimum energy crossing point, very clearly mentioned in theoretical works by Vanquickenborne and Ceulemans [START_REF] Vanquickenborne | Ligand-Field Models and the Photochemistry of Coordination Compounds[END_REF], that leads the system to the ground state PES of a pentacoordinate, Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184 electrophilic, 16-electron coordinatively unsaturated species. Singlet geometry optimization from 3/1 MECP(P) results in a shortening of the Ru-N bond to the κ 1 -btz ligand and full relaxation to a square pyramid GS(P) displaying a bare face with a vacancy available for nucleophilic attack by the entering ligand on the face opposite to the κ 1 -btz ligand, thus leading to the trans intermediate photoproduct shown on Scheme 4. Note that pentacoordinate intermediates have also been described in the framework of photoreactivity studies on iron [89][90] or chromium [START_REF] Żurek | Photostereochemistry and Photoaquation Reactions of [Cr(tn) 3 ] 3+ : Theoretical Studies Show the Importance of Reduced Coordination Conical Intersection Geometries[END_REF] complexes. In this project, a combination of geometry optimizations, relaxed surface scans and NEB calculations to connect all triplet states has enabled us to propose a full reaction mechanism for the formation of the trans intermediate photoproduct.

Generalization: a return to Ru(bpy) 3 2+

From the early 1970s [Ru(bpy) 3 ] 2+ has been intensively studied for the luminescent and electron and energy transfer properties of its long-lived 3 MLCT excited state [START_REF] Juris | Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence[END_REF]. Meanwhile, its photostability was challenged in the presence of coordinating anions such as SCN - [START_REF] Hoggard | Photoanation of the Tris(2,2'-bipyridine)ruthenium(II) Cation by Thiocyanate[END_REF] and Cl - [START_REF] Van Houten | Photochemistry of Tris(2,2'-bipyridyl)ruthenium(II) in Aqueous Solution[END_REF] to form Ru(bpy) 2 X 2 photoproducts following the loss of one bpy ligand, thus involving some dissociative excited state that is presumably of metal-centred character. The population of 3 MC states could be enhanced under high laser power excitation in water [85],

although the dominant excited state decay route remained reformation of starting material [Ru(bpy) 3 ]Cl 2 . Under more classical excitation conditions, Hauser and coworkers did not observe population of the 3 MC state of [Ru(bpy) 3 ](PF 6 ) 2 , whether by ultrafast transient absorption spectroscopy following excitation in CH 3 CN at 400 nm [START_REF] Sun | Experimental Evidence of Ultrafast Quenching of the 3 MLCT Luminescence in Ruthenium(II) Tris-bipyridyl Complexes via a 3 dd State[END_REF] or by TR-IR in Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184 CD 3 CN or KBr pellets [START_REF] Sun | Ultrafast transient IR spectroscopy and DFT calculations of ruthenium(II) polypyridyl complexes[END_REF]. On the other hand, using excitation at the same wavelength but in dichloromethane solution, Onda et al. reported the observation of the transient 3 MC state of [Ru(bpy) 3 ]Cl 2 and based their reasoning on the 1600 cm -1 region of the TR-IR spectrum [START_REF] Onda | Observation of the dark state in ruthenium complexes using femtosecond infrared vibrational spectroscopy[END_REF] [START_REF] Mukuta | Direct Observation of the Coord[END_REF]. All in all, the observation of relatively inefficient photoreactivity of [Ru(bpy) 3 ] 2+ , but only under certain conditions, and the glimpsed spectroscopic characterization of its 3 MC state (or lack of characterization) illustrate the complexity of this case and requirement for further investigations.

Having identified new 3 MC states displaying peculiar flattened geometries with one single bidentate btz ligand repelled for [Ru(bpy)(btz) 2 ] 2+ [START_REF] Dixon | Theoretical illumination of highly original photoreactive 3 MC states and the mechanism of the photochemistry of Ru(II) tris(bidentate) complexes[END_REF], we embarked on a search for similar structures on the 3 PES for [Ru(bpy) 3 ] 2+ itself. With a suitable guess geometry based on the identified key structural parameters we indeed found that a similar flattened 3 MC state is also a local minimum for this archetypal complex. In this novel state, which we call 3 MC cis (due to the elongation of two mutually cis Ru-N bonds), the highest singly occupied molecular orbital is d x 2y 2 -like, whereas it is d z 2 -like in the now 'classical' 3 MC state identified earlier in Section 2, which we now call here 3 MC trans (as it displays two elongated trans Ru-N bonds, Figure 7).

In this new nomenclature the Ru(II) btz states shown on Figure 5 3 MC(A/B) are of the 3 MC trans type, while the flattened 3 MC(F) state is of the 3 MC cis type. Both states are only 2 kcal/mol apart, and the conversion from one to the other is essentially barrierless (Scheme 5) [97]. In addition, the activation energy to populate them from the lowest 3 MLCT state is similar (9 kcal/mol for 3 MC trans vs 10 kcal/mol for 3 MC cis ), which means that both 3 MC states are likely to be populated. At this stage it might be tempting to assign a preferential role of phosphorescence quencher to the classical 3 MC trans , while the novel 3 MC cis would be more prone to photoreactivity and particularly bpy loss. However, what one can also note with confidence at this stage is the observation that the 3/1 MECP for the newly identified 3 MC cis state lies 3 kcal/mol lower in energy than that for the established 3 MC trans state and thus this previously unknown 3 MC state will inevitably play a prominent role in the photophysics of this most famous of chemical compound. We are currently actively working on exploring the photochemical fate of these two distinct 3 MC states and will report these results elsewhere in due course.

Conclusions and Outlook

Over recent years our joint projects and the combination of our synthetic, spectroscopic and theoretical skills have led us to discover most exciting and intriguing features regarding triplet [START_REF] Scattergood | Labilizing the Photoinert: Extraordinarily Facile Photochemical Ligand Ejection in an [Os(N^N) 3 ] 2+ Complex[END_REF]. Clearly, the trans photoproduct formation pathway for this Os(II) complex should also involve flattened 3 MC cis -and 3 MC(P)-like states.

What our results reveal is the importance of not only identifying all possible 3 MC states on the 3 PES of a given complex as well as their relative accessibility from the 3 MLCT state, but also the minimum energy paths that connect them to each other and the relative accessibility of minimum energy crossing points to singlet ground state surfaces of both the reactant and photoproducts (Scheme 6). A further step would be to investigate the preferential relaxation paths of the systems by excited state dynamics, as only certain specific 3 MC states are productive towards ligand loss. This additional knowledge and understanding enables a far deeper rationalisation of experimental observations and microscopic mechanisms, but will also provide predictive tools which will give the synthetic chemist the ability to confidently control and fine tune photochemical behaviour with the aim of influencing selective 3 MC population to achieve efficient photorelease. No doubt the refined view that we currently have of the 3 PES topology will soon have to be updated. The photochemical transformations observed in Ru(II) bis(bitriazolyl) complexes, for example, has led to enlightening insights on possible processes operating on the lowest 3 PES. Beyond these immediate systems this has led to further fundamental insights of much broader significance in other very well-known systems. Whilst mechanistic details for the formation of the trans intermediate κ 1 -GS photoproduct from tris-chelate complexes have been elucidated [START_REF] Dixon | Theoretical illumination of highly original photoreactive 3 MC states and the mechanism of the photochemistry of Ru(II) tris(bidentate) complexes[END_REF], the equivalent details regarding the far more common formation of cis photoproducts from chelate ligand release have yet to fully determined and are the subject of ongoing research in our laboratories. In this regard we can expect great insights from the improved theoretical methods described here combined with ultrafast spectroscopies, particularly the most recent developments of ultrafast time-resolved X-ray spectroscopies [START_REF] Chen | Recent advances on ultrafast X-ray spectroscopy in the chemical sciences[END_REF][105] [START_REF] Kjaer | Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy[END_REF] enabled by free electron lasers.

Figure 1 .

 1 Figure 1. (a) Jablonski diagram depicting the ground and excited states of a [Ru(bpy) 3 ] 2+ -like complex (key processes: a photoexcitation, b intersystem crossing, c radiative deactivation, d internal conversion, e non

(

  from almost parallel to almost perpendicular surfaces) are important to the efficiency of nonradiative deactivation[START_REF] Harvey | Computational Studies of Reactivity in Transition Metal Chemistry[END_REF][START_REF] Malhado | Non-adiabatic transition probability dependence on conical intersection topography[END_REF].

Figure 2 .

 2 Figure 2. Structures of [Ru(bpy) 3 ] 2+ and [Ru(tpy) 2 ] 2+ .

  . Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

Figure 6 :

 6 Figure 6: Examples of pentacoordinate 3 MC state, 3/1 MECP and singlet ground state with key Ru-N distances and smallest trans N-Ru-N angles of the approximate square-plane [87].

Figure 7 .

 7 Figure 7. Classical trans-elongated 3 MC trans state and novel cis-elongated 3 MC cis state of [Ru(bpy) 3 ] 2+ with most significant Ru-N elongations and their SOMO+1 [97].

Scheme 5 :

 5 Scheme 5: Minimum energy paths, energy barriers and energy gaps for the 3 MLCT-3 MC trans , 3 MLCT-3 MC cis and 3 MC trans -3 MC cis internal conversions of [Ru(bpy) 3 ] 2+ [97].

Scheme 6 :

 6 Scheme 6: Our current schematic view of the elementary steps and intermediate states populated along the photoinduced release of a bidentate ligand towards the formation of a given final photoproduct. The purple arrows represent solvent capture (S = solvent). In the case of multiple photoproducts (eg cis and trans isomers), additional states and bifurcations should be involved. For the sake of clarity, only selected interconversions are shown.

  Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184 excited states of Ru(II) complexes. 'The 3 MC state', a denomination that pervades the literature, actually covers an expansive region of the 3 PES displaying several local minima to which we tentatively assign preferential roles as photophysics and photochemistry quenchers and/or promoters.Our recent work has identifed highly novel flattened3 MC states as being intimately involved in trans photoproduct formation. In fact, looking back on one of our previous studies on photoisomerization mechanisms, flattened3 MC states had made an appearance but we did not appreciate their full significance at the time[START_REF] Göttle | Adiabatic Versus Nonadiabatic Photoisomerization in Photochromic Ruthenium Sulfoxide Complexes: A Mechanistic Picture from Density Functional Theory Calculations[END_REF]. Having then found some in [Ru(bpy) 3 ] 2+ itself, such distorted states seem to be a common feature in Ru(II) coordination compounds, and possibly in coordination chemistry in general since flattened MC states have been recently described for other metals (Fe[START_REF] Feng | Triplet Ground-State-Bridged Photochemical Process: Understanding the Photoinduced Chiral Inversion at the Metal Center of [Ru(phen) 2 (L-ser)] + and Its Bipy Analogues[END_REF], Ir[START_REF] Jacquemin | The short device lifetimes of blue PhOLEDs: insights into the photostability of blue Ir(III) complexes[END_REF][100][START_REF] Escudero | Mer-Ir(ppy) 3 to Fac-Ir(ppy) 3 Photoisomerization[END_REF]) as well as for the cis-trans isomerization of [Ru(bpy) 2 (PMe 3 )(OH 2 )] 2+[START_REF] Rojas Pérez | Cis-Trans Interconversion in Ruthenium(II) Bipyridine Complexes[END_REF]. We have recently reported the remarkable and unprecedented photochemical reactivity of the Os(II) complex [Os(btz) 3 ]

2+

, which in acetonitrile yields both cis and trans isomers of the photoproduct [Os(btz) 2 (NCMe) 2 ] 2+ with observation of both cis and trans ligand-loss intermediates [Os(κ 2 -btz) 2 (κ 1 -btz)(NCMe)] 2+

  Coord. Chem. Rev. 2020, 408, 213184. https://doi.org/10.1016/j.ccr.2020.213184

Acknowledgements

We thank the French Ministry for Higher Education and Research for a Ph.D. fellowship to A.S. The French contribution to this work was performed using HPC resources from CALMIP (Grant 2018-[p1112]). Some of the work in the Elliott group covered in this review involved use of computational resources via his membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202, EP/R029431), and we therefore wish to acknowledge the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk).

Supporting information

Animations along the 3 MLCT-3 MC minimum energy path for [Ru(bpy) 3 ] 2+ : geometries, highest SOMO (dπ) and SOMO+1 (π* followed by dσ*).


Luisa Fernanda
email: luisafrv@gmail.com

Rodríguez Valbuena

Industrial Engineering Education Field in Colombia

Keywords: Industrial engineering education, Bourdieu field's methodology, social structures and practices

This paper analyze the professors narratives of different industrial engineering programs in Colombia, seeking to answer research question about the characteristics of configuration processes and transformation of industrial engineering education in the country, the methodology used was Bourdieu's fields, from the habitus concept of professors while they are the education's field agents. The study was approached from the analysis of social practices, in which more than mass events of a structural nature, it seeks to strengthen the collective memory of those who have been excluded from official history and serve as an educational space from study of processes and events that led to formation of social subjects, investigating the interaction and conflicts, in such a way that the past can be questioned according to current emancipatory projects. The configuration and transformation processes of industrial engineering as a knowledge discipline in Colombia between 1950 and 2000 were studied through the tensions and ruptures, the conflicts and new interactions generated from the developed world discourses. Critical analysis was considered as the best alternative in information treatment, because it facilitated the professors' narratives analysis. For processing information it was utilized QDA (qualitative data analysis) y GEPHI (graph visualisation and cartography in data mining).

Introduction

The accession of the capitalism and the industrial strengthening that gave beginning to the production in mass and determined the need to adopt new forms of rationalization of the work, from the implantation of the development model, about 1950; an untimely managerial summit took place in Colombia that shot the demand for education in these areas, and motivated a new social division of the work.

In 1958, birth the first Industrial Engineering Program in Universidad Industrial de Santander (UIS) the teachers were coming from the careers of Chemistry and Chemical Engineering of the same university. In the same year, with the accomplishment of the first seminar of Scientific Administration, there is created the Instituto Colombiano de Administración -INCOLDA -that gave like proved the creation of the Career of Industrial Administration of the Faculty of Mines, now it annexes to the Universidad Nacional sectional of Medellin. In 1960 believe itself in Medellin the Escuela de Administración, Finanzas y Technología -EAFIT -and there is established the career of Industrial Engineering in Universidad de Los Andes. Hereby, the university device of the country was adjusting to industry requirements, which was coming applying the principles of work rationalization: the trades description, times and movements of the work, the cost measure is necessary of every operation and establishment of work standards and production incentives.

During the 70s years as a result of the United Nations for the Development PNUD technical cooperation project, that which sought to direct top education to the occupational and technical thing as base of the economic growth, the increase arises for the demand of careers that are relatives with the administration of the industrial technology (specialized engineering), since it was the case of the industrial engineering, with the administration and 'rationalization' of the State´s economy and of the private company (economy and relatives disciplines) searching of answers to the social demand for education and for solution of the social problems derived from the new form of economic growth.

The processes of rationalization that gave origin to the industrial engineering in Colombia and then those of Bourdieu's field theory contributed theoretical substratum from which there are analyzed the diverse tensions that gave origin to the discipline, likewise, the notions on subjectivity of Foucault, while, with the restoration of the development speech, the educational expansion, the urbanism and the industrialization during the consolidation of the modernization, in the second half of the 20th century in the country, were imposed and appropriate new speeches and fields of knowing, as that industrial engineering.

The conformation of the social specific fields of every discipline of knowing or profession, as that of the industrial engineering they serve to realize of the degree of inculcation or permanence of a specific habitus, produced in the disciplinary processes of reproduction, carried out in the social university space. Or saying of another form, the conditions and characteristics that favor the emergence of the processes of reproduction, for the speeches that it creates, turn also into the possibility conditions of the discipliner social field.

One of the decisive events in the structure of these new discursive objects, constituted it the appearance of the modernity notion in the moment itself of capitalism consolidation and the appearance of technology notion in the economic field, Weber for example, who emphasizes the value of technology in exaltation of the capitalist spirit in Europe at ends of 19th century, whereas Marx defines the process of simple accumulation as condition of existence the capitalism that characterized the modern world. And Touraine for whom the instrumental rationality bases of the capitalism, which defined the industrial companies, is sustained in the technology, which began to the fret with the objective rationality of the sciences.

Other studies like [START_REF] Vásquez | el discurso filosófico de la modernidad y la crítica a Foucault[END_REF]) make a Foucault´s analysis of the archaeology offer that on having delimited the margins, the edges, the excluded from the speech, which the history has not used, allows to see the fissures and the problems in the constitution of the human sciences and reveling his instrumental rationality as offer of illustration and as practice of slavery. This rationality carries Foucault to placing the conformation of the subjects in the power / know dispositive, in the technologies of domination and in a detailed consideration of the modern individual as product of a multiplicity of dividing and individualizer technologies, of subordination -subjectivity, questions traditionally ignored by the macrotheoretical perspective of the social critical science.

This study raises also that the Foucault´s analysis, it allows to contrast like in the study of Habermas's communicative action, there exists a devaluation of decisive elements for the analysis of the modern relations of power, that surely Habermas, in reason of his loyalties to the theories of Austin and Searle´s "speech-act" , attributes to them a character idealistic and neutral in excess, disregarding the effect of the bodies administration in the relations power of modern society, when this might constitute an enrichment of perspective to the communication theories.

Industrial engineering as a discipline responsible for the management, planning and control of resources in an organization, that being based on the principles of economic rationalization, would have its origins in the implementation of industrial capitalism in our context and would be associated with the installation time of development speech during the period of modernization in the second half of the twentieth century. This paper is an invitation to make a different reading of the events that brought about the development and the idea of progress that was inserted immediately in the minds of those who were recognized as underdeveloped at that time, especially in technical and management areas like industrial engineering.

Configuration of Industrial Engineering Education Field

All configuration process starts from the analysis of the facts that characterize and give shape to a notion or concept that prior to said facts did not exist, that is, it is the study of the processes that favor the appearance of a concept, in our case it was split of the historiographic analysis of the processes that gave rise to the education in industrial engineering to focus on this aside in making the logical construction of the field concept of industrial engineering education from the notions of habitus and field contributed by Pierre Bourdieu, eventually will be made use of power and discipline notions from Foucault, as guides in the analysis and understanding of process.

Thinking in terms of fields is to think relationally: they are structured spaces of positions, to which a number of properties are linked, that can be analyzed independently of the characteristics of those who occupy them. A field is defined, among other things, by what is at stake and its specific interests, which are irreducible to the commitments and interests of other fields. Each field engenders the interest that is its own, which is the condition of its operation and is composed of people who share the game and is willing and able to play it.

Thus, thinking about the social field of industrial engineering education is to be located in the university social space, in the daily work of its agents, professors, deans, directors and students of an industrial engineering program, structured by the interests that these agents put into play, by the strategies they use to position themselves in the same and by the relations of force generated within them, generating inequalities and ruptures in the exercise of power, blurring and hiding it. This field, which is structured by the force relations engendered by its agents by making use of their accumulated capital as differentiating and stratifying strategies that blur and create different forms in the exercise of power, is in turn the structuring of these same agents because it establishes the emergency conditions of their habitus and durable dispositions.

Social capital is the differentiating principle of social fields, Bourdieu liberates a concept from the economic connotation itself and extends it to any type of good susceptible to accumulation, around which it can constitute a process of production, distribution and consumption, and for so much, a market. In this sense, social fields can be considered as specific capital markets. That is, not everything you need is necessarily a field, it has to be a valued, sought after, that, being scarce, products for its accumulation, that achieves a certain division of labor between those who produce it and those who consume it, between who distribute it and who legitimize it. In other words, it has to constitute a market around that good so that a specific field emerges.

Cultural capital is linked to knowledge, science, art, and is imposed as an indispensable hypothesis to account for inequalities in school performance. Cultural capital, as (Gutiérrez, 2006, p.37) describes it, can exist under three forms: in an incorporated state, that is, in the form of durable dispositions (habitus), with a type of knowledge, ideas, values, abilities, etc.; in objectified state, in the form of cultural goods, paintings, books, dictionaries, instruments, etc.; and in an institutionalized state, which is a form of objectification, as is the existence of different school titles, this leads to the existence of social institutions that are recognized as having the legitimate capacity to administer that good. These are institutions of consecration and legitimation specific to the field, stories such as the University, and their appearance and permanence are closely related to the same field activity and their relative autonomy.

In Colombia, knowledge-power field in industrial engineering is based on the diversification and stratification processes characteristic in second middle of twentieth century -the capitalism consolidation period in our societies-. The establishment of the modernization model that involved the removal of all the infrastructure required to carry out the extraction of our natural resources; urbanism: that forced the displacement of large numbers of people from vast rural regions and their concentration in small urban centers; industrialization: which, accompanied by large infrastructure projects, employed large quantities of labor, with clearly differentiated and hierarchical levels and with imported technology, which led to the hiring of foreign professionals specialized in its installation and operation, a phenomenon that increased even more the stratification between the different levels within the newly created industries and; schooling: from which, educational institutions were created and diversified with the new demands for education of the different levels of labor employed. All these processes gave rise to the social division of labor in different layers and social nuances.

The imposition of the development model in our societies obeyed the need to increase and improve the production of the "developed world", in such a way that it made necessary the social division of work around these new functions created and / or specialized from the model, university was reformed to meet this requirement.

In this sense, as explained by (Vasconi, 1975, p.15) the demand for technical training for work is something "objective" within the development of the productive forces, does not depend on the dominant mode of production and therefore does not fall within the division social of work. Contrary to what happened in our education, in which Proceedings of the International Conference on Industrial Engineering and Operations Management Paris, France, July 26-27, 2018 © IEOM Society International our society being governed by the private and extractive interests of the developed world, this "objective demand" depended on the social division of labor and the organization of production and not on the technical division of work, as it should have been.

Culture then has a nature of exchange value through the transmission of school knowledge, which operates thanks to the selection in the system of diplomas. Education is produced by its exchange value and not by its use value. Thus the school system is supported by the legitimacy of an unequal's hierarchy. The merchandise of instruction is inextricably linked to the system and is presented as the fundamental instrument of its reproduction. In this logic, the level of educational achievement is defined by the academic credential that is acquired.

All of above allows identifying a field of industrial engineering education marked by the strategies of both diversification and hierarchy resulting from the social division of labor characteristic of all modernization processes carried out in Colombia since the mid-twentieth century, where main but was the production of academic credentials of different value and the reproduction of unequal subjects. In this way knowledge is produced only in terms of its exchange value and not its use value, therefore, we find an industrial field lacking its own technological developments that nurture innovation and learning processes in the educational field.

Some authors like (Escobar, 1996, p.113) emphasize the emergence of the development concept after the second postwar period; it was initially formulated in the United States and enthusiastically accepted and improved by the elites and rulers of the Third World, from then on. According to Escobar, total of the cultures and social formations of three continents were transformed according to the dictates of the so-called First World through a process known as "modernization".

Both Martinez and Escobar agree that the nascent order of capitalism and modernization, inserted in our societies after the discourse of development, depended on a policy of struggle against poverty rather than industrial and technological power, whose intention was not only to create consumers, but to transform society, converting the poor into objects of knowledge and administration. Poverty was associated with traits such as mobility, vagrancy, independence, frugality, promiscuity, ignorance, and the refusal to accept social duties, to work and to submit to the logic of expanding needs. Therefore, the administration of poverty demanded intervention in education, health, hygiene, morality, employment, teaching good habits of association, saving, raising children, and so on. Economic growth presupposed the reproduction in poor countries of the conditions that characterized the advanced capitalist countries (including industrialization, urbanization, agricultural modernization, and infrastructure, the growing supply of social services and high levels of literacy).

With imposition of development model the modernization process seized by the United States in the midtwentieth century in Latin America were introduced into our societies notions such as mass production and consumption and the consequent appearance of the disciplines responsible for carrying them out such as industrial engineering, later, with the decline of socialism in the world, the model of modernization assumes new forms and is transformed into that of globalization and the discourse of development is nourished by new content such as selfmanagement and self-sustainability. The speeches for the education in industrial engineering are also filled with new concepts and begin to favor highly productive production processes that respect the environment and the training of independent liberal professionals or entrepreneurs.

Habitus of industrial engineering professors

By habitus, Bourdieu understands the set of generative schemes from which the subjects perceive the world and act on it. These generative schemes are generally defined as structured structuring structures, they are socially structured because they have been shaped throughout the history of each agent and involve the incorporation of the social structure, of the concrete field of social relations in which the social agent has been conformed as such. But at the same time they are structuring because they are the structures from which the agent's thoughts, perceptions and actions are produced. This structuring function is based on the processes of differentiation in terms of the conditions and needs of each class.

Modernizing forces such as urbanism, industrialization and schooling that made available to the agents and institutions that were creating or affecting their passage, new discourses and forms of subjectivity, that motivated different social practices in the subjects involved and new forms of knowledge circulation, in the creation of new habitus that according to Bourdieu account for the degree of inculcation achieved once the pedagogical action ceases, by the internalization (subjectivation) reached such as to guarantee its application in practice. Paris, France, July 26-27, 2018 © IEOM Society International Industrial engineering becomes one of those new forms of disposition or habitus that "it was necessary" to assume the agents responsible for industrialization, to "become necessary" the application of Taylor's principles of economic rationality in the newly created factories, which very soon they were constituted in organizations that produced a wide spectrum of goods and services and then they were denoted with the distinction of companies, becoming an object of schooling knowledge and therefore a new discipline.

The principles of efficiency and productivity on which the economic rationality of the industrialization process is based, became the main capital and constituent element of the habitus or action domain of the industrial engineer.

The social space of the post-war university in the new developed society assumes the responsibility of integrating knowledge into the productive world to guarantee the scientific and technological progress that would allow the long-awaited progress and economic growth in the country and the industrial engineering education field, then arises at the heart of this structure to be configured at the intersection of capital, work and knowledge represented by universities and all instances of it.

To know the constitutive elements of habitus, the social capitals that configure them, know about their processes of conceptual construction around the purposes of training, the characteristics of the curricula and the scope of the regulatory frameworks in their institutions, it was considered fundamental to analyze the distinctions that professors make in their academic practice, from the direct observation of the institutional contexts of industrial engineering programs and their experience as educators. For this, three universities were chosen.

In the study of the concept of habitus as structuring and structured from social practices, the starting point of this theory is the abandonment of the classical distinction -developed strongly in behavioral approaches-between subject and object. In effect, from the notion of habitus it could be affirmed that there is no distinction between the external and internal universes of the individual (or the group), in the process of discursive construction. The subject and the discursive object are not fundamentally different. This object is inscribed in an active context, partially conceived by at least the person or group, as a prolongation of their behavior, their attitudes and the standards to which they refer. In other words: the stimulus and the response are inseparable. They are formed together. Strictly an answer is not a reaction to a stimulus. It is to some extent at the origin of it. That is to say, that this is largely determined by the response.

In the social sphere, the habitus has a functional aspect by giving meaning to the behaviors of individuals or groups in a way that allows them to understand reality from their frames of reference, and adapt and define a place for themselves; that is, an identity. In addition, it constitutes a guide for action, guides social dispositions and, at the same time, makes it possible to determine anticipations and expectations about it.

If, for example, an individual (or a group) expresses an opinion (that is, a response) about an object or a situation, that opinion is in some way constitutive of the object, determines it. The object is then reconstructed from the opinion, in such a way that it is consistent with the evaluation system used by the individual. That is, by itself an object does not exist. It is and exists for an individual or a group and in relation to them. Thus, the subject-object relationship determines the object itself.

Social practices are collectively constructed, oriented and generate behaviors. In this sense, the study of the social practices of the professors of industrial engineering would express the changes produced by the processes of modernization and the labor flexibilization experienced in the space of the universities from the middle of the last century.

The analysis and interpretation in the social practice, during the academic work allow understanding the interaction and connections between the individual and the social conditions in which the university professors change; At the same time, understand the processes given in the socio-cognitive adaptation of university professors to everyday realities and their social and normative environment.

Reflection on questioning: What are the constitutive elements of the habitus university professors trained in the field of industrial engineering or in the field of industry in Colombia, from its beginnings to the present, about the realization of academic work in the universities? It was carried out from the content analysis of interview texts as hermeneutic units from Bourdieu's habitus perspective, for whom distinctions elaborated or induced in situations of interaction, such as interviews, play a frequently more important role than adopted by the subjects in the groups.

The study of relationships in practices leads to the double problem of articulation and interaction between the different constitutive fields of social reality. In other words: if it is found and admits that the habitus determines behavior, what role do they play in the elaboration of effective social practices, that is, in complex systems of action socially invested and subject to social and historically determined challenges? The analysis of the content of the interviews carried out with the professors intended to orient a panorama from which to read what they think, how they think and how they are represented in the field of industrial engineering in Colombia.

Proceedings of the International Conference on Industrial Engineering and Operations Management Paris, France, July 26-27, 2018

© IEOM Society International

For the study of the dispositions of the professors of industrial engineering, the notion of habitus as a sociocognitive set, organized in a specific way and governed by own operating rules.

Resultants

From the critical-hermeneutic (deconstructive) historical research methodology used in this paper work (Foucault, Deleuze and Escobar's work on the deconstruction of development), history is conceived not as a linear set of succession of events ordered in time, history is read as a social process, from its ruptures, from the traces, from the edges that reveal its existence and discourse, in which the concepts emerge from the practicality or the conditions of possibility that donate to the process.

Deconstruction-interpretative (historical-hermeneutic), assumed from the theoretical construction made from the structuralism school (Bourdieu, Durkheim, Weber and Foucault) distinctions or notions emerge from the search from the edges, from the unspoken, from the footprints that the process leaves in the minds and discourses of the subjects, that to not be explicit, makes that the method seeks to explain them and to achieve it makes use of constructed theory, in a process that is not ordered, nor linear, in the concomitant dialogue between it and what was said to make explicit what was not said.

In the present study, a program was used for the graphic and statistical analysis of complex systems (data mapping) called Ghephi, the mapping of the data in a graphical network, it is a procedure that allows to disaggregate and measure in a statistics the levels of interaction of the elements in a situation or phenomenon, in any field (social, natural, technological, productive, market, etc.).

From the information obtained in the data cartography it is easy to make the interpretation of the phenomenon and make decisions about it. The statistical principle on which the data cartography is based is the clustering analysis, based on the study of the modularity or topology of the network or structure of the database, that is, the concentration in groups and interactions, clearly differentiable. From the concepts expressed by the professors of industrial engineering during the interviews through the use of the Ghephi program, the analysis network was built.

Modularity is a statistical measure of the structure of networks or graphs. It was designed to measure the strength of the division of a network into modules (also called groups, groupings or communities), through the analysis of clustering. Networks with high modularity have solid connections between the nodes (in our case it is about the concepts or words used by teachers during the interview) within the modules or groups. Modularity is often used in optimization methods for the detection of the community structure of networks. The three groups of words or modules with modularity of 0.652, which were identified within the structure with the help of Ghephi program and in the light of field's theory, from the notion of habitus, allowed for validate the categories of analysis:

First group it presents the notions from which the professors understand the processes of configuration and transformation of industrial engineering as a field of knowledge in Colombia. (Category: "Configuration of industrial engineering as a field of knowledge") Second group seeks to account for the constitutive elements of the habitus of industrial engineering professors and serve to characterize these professors. It is analyzed from the notions that according to them constitute the task of the professor of industrial engineering (Category: "Professors of industrial engineering education field ") Third group, interspersed with the first, but that arises from some unusual concepts such as this one of "deindustrialization" analyzed in the theoretical corpus as an answer for possible other discourses from which to read for the discipline. (Category: "Others speeches for industrial engineering education in Colombia") It is easy to observe from Figure 1, how the frequencies greater than 100, correspond to First group related to the configuration processes of the discipline, the Second group between 100 and 10, they constitute notions would allow to characterize the industrial engineering professor´s habitus and there would be Third group of some unusual terms with frequencies less than 10 such as "deindustrialization", which would arise in response to the question about possible speeches or other speeches for industrial engineering based on its beginnings the development discourse in mondialization model. The three groups of concepts are also coincident with the three research categories. After entering the table of frequencies and their relative relationships developed from the QDA (Qualitative Data Analysis) Miner program, presented in Figure 1, we proceeded to define the central core of the interviews conducted content, which is presented in the Figure 2, identified by the Gephi program, this scheme allows visualizing the three groups mentioned, corresponding to the three categories of analysis and the peripheral elements that constitute them. These elements also hint at the themes identified within each category. Engineering and Operations Management Paris, France, July 26-27, 2018 © IEOM Society International

Figure 2. Central nucleus of interviews content

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Professor's distinctions about configuration of field

This section analyzes the different accounts of the industrial engineering professors interviewed, seeking to analyze what constitutes for them the processes of configuration and transformation of industrial engineering as a field of knowledge in Colombia, and based on the comparison with the theoretical corpus, giving an answer to it.

We understand by configuration processes of industrial engineering education field in Colombia, to the group of phenomena that propitiated the appearance of industrial engineering like studies plan in the faculties of engineering, which have been transformed or they have stayed in agreement with the postulates of the development model and that have favored or prevented its consolidation as a discipline within the total of engineering.

In the analysis made from the QDA program to the texts of the interviews, it was possible to identify the First group of central elements of professors narratives, as well as a large number of peripheral elements that constitute the category of industrial engineering configuration processes as a field of knowledge in Colombia, within this, you can identify three central nodes (words) that agglutinate most concepts: <engineering>, <industrial> and <make>, around which the other peripheral elements are interwoven . These nodes constitute this category and allow visualizing, what professors think about industrial engineering in Colombia and its configuration processes.

The first constituent element of the central nucleus of the professors' habitus, with the highest degree of centrality, is the <industrial> notion (Figure 3), it is constituted in a notion that agglutinates other peripheral elements in turn important, such as < university>, <development>, <productive>, <education> and <organization>, which exercise the concretion function of nucleus.

Figure 3. <industrial> notion

The second central element of professors' habitus, is the notion of <engineering> (Figure 4) Along with the notion of <industrial> they constitute the normative dimension of the dispositions that the professor has in front of his academic practice with his students . It is associated with other peripheral elements such as <school>, <training>, <study>, <epoch>, <before>, <programs>, <subjects>, <idea>, <general>, which have the function of concretion of the central nucleus, insofar as they refer to concrete facts experienced by professors, but they also exercise the function of regulation insofar as they account for the transformations perceived by them about the environment of industrial engineering in Colombia. This definition makes clear that the industrial engineer intervenes on production systems (integrated by men, machines and other resources) and that it uses scientific and social knowledge to operate in said systems. But nevertheless, as announced in the introduction, it directs all the content towards the achievement of the ends, underestimating the means, in this case the fact that the industrial engineer intervenes in social systems, leaving aside the study of the actors, their interests and knowledge and the ideologies or policies that frame any intervention in the social.

The document on the specifications for the (ECAES test, ICFES-ACOFI) industrial engineering sufficiency test in Colombia establishes the minimum contents that any industrial engineering program should have, reducing the field of action of the professor in this discipline, to three specific areas:

1. Basic Sciences: Mathematics, Physics and Chemistry 2. Professional: Production and operations research. 3. Complementary areas: Organizations, Economy, Markets, Finance and Humanities

The humanities are considered as complementary areas of support to the central nucleus of the formation, which, since they are not directly linked to it, are reduced to a decontextualized course without major impact. That is why teachers' accounts focus on practical notions from the <make> and their concepts associated with practice, such as machines, processes, factory, company and production, management or design; the reason for being industrial engineering professors and their work (habitus) reduces it to that context.

Habitus of Professors

For analytical approach of academic work of professors were used habitus and dispositions notions from Pierre Bourdieu. "The habitus is the substratum of the everyday, in which men and women "say" and "speaks" their existence; being the everyday for the individual his most private space, but simultaneously the most public". This notion guided the analysis of the teachers' stories because it allows them to be located within their work from their own histories and life trajectories.

This Second group or cluster of relationships as central element of professors' habitus, is functional in nature, refers its daily life, social, cultural and symbolic capitals and your aspirations. It is expected to observe how one of the most repeated words in the teachers' discourse is <I> and <myself> (Figure 7), habitus is structured from the experiences lived by each one, from their lived histories converted in practices, they are the social class made body and to that extent, denote the high degree of self-esteem that has these teachers and the conviction they have that the work they perform is very important, characteristic equally observable in most teachers regardless of the discipline in which they move, in general it could be said that teachers, especially university teachers have a very good image of themselves, which would be a fundamental part of their habitus. The notions that surround the word < I > make the role of peripheral elements, they exert the defense function of the central core of professors habitus, because it is through themselves exemplification and of their lived experiences that they support and defend their postulates. In the teachers' explanations, each one from his family trajectory and his personal experience, his values, skills and knowledge exposes how and why he chose to be an industrial engineer and later become a teacher, letting us see how they shape their habitus and what they become accumulated social capital to be able to play inside the field. Within professor's discourses arises also the regional origin thematic, that according to Everett Hagen, it depends largely on the social groups and cites characteristics. In the case of Antioqueño's entrepreneurship, determined by Moorish migrations influence and geography of region, these regional characteristics professors convert into accumulated social capital in durable dispositions form from the values and skills incorporated into the habitus.

The subjectivation processes carried out by professors in their habitus conformation, these processes are reproduced so that students have the same effect. Instrumental rationality present in useful sciences, such as mathematics or statistics, bases of industrial engineering, it works as a normalization device preventing critical reflection and paralyzing the collective capacity and solidary action of subjects, keeping them isolated, immersed in productivism/consumerism desire to increase their profits. Reflection of this is the almost absolute absence of questions or criticisms made by the professors regarding the way of doing industrial engineering.

Contrary to happens with human and social areas in public institutions characterized by maintaining an spirit of criticism against notions such as development, progress, growth, competition, and internationalization; engineering areas in the same institutions are characterized for being less critical and complacent with government policies that promote the interests of foreign exploitation companies, in many cases. Most professors interviewed give meaning to industrial engineering practice from these processes, there were some who tried to criticize the discourse on productivism, however, they fail to be forceful in their position to present as favorable the whole process of industrialization and extraction of natural resources, without further questioning, About internal dynamics in academic work, most of the professors practice self-care, practice exercise, except for retired professors, who for their advanced age do not, for the majority of non-retired professors, their work schedules are quite tight because they must fulfill diverse academic responsibilities distributed between administrative, teaching and investigative functions. Mostly of them describe the ways in which they assume their work and the procedures they use during the same, from practical case studies methodology, of that, students themselves construct and solve based on an existing literature, teacher' work is displaced by the facilitator' one, giving authority for knowledge construction of to the authors' texts, which are generally translations of English manuals based on rationality principles of development that governs the discipline. They reveal the degree of dependence on the knowledge imparted during the academic practice, denoting the absence of the teacher's voice within it, to the point that the same teacher complains about his absence and rewards the self-taught student, who builds his objects of study from the literature available, denoting another mondialisation model characteristics, that operates from normalization and standardization of products, including education, which is delivered as standard packages ready to consume. Engineering and Operations Management Paris, France, July 26-27, 2018 © IEOM Society International A constant in the problems revealed by teachers during the exercise of their work was the economic problem, from the difficulties of not having sufficient resources, which prevents access to information, such as subscription to journals or databases to meet the academic production standards that each teacher must cover. From the need to provide income to their institution from different activities related to research, extension and management of various resources, including the boost to enrollment, however, some express satisfaction with this way of academic production, incorporating all this doing to their habitus and converting it into social capital.

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Regarding the difficulties in student motivation, professors highlight the difficulty in mathematics area and make it look like a challenge to overcome in order to be recognized as engineers, as a hard test that they as students must have approved and that their students must also approve. Recall that education in useful sciences (mathematics and its derived disciplines such as engineering) is one of the most effective strategies for disciplining and normalizing the population because it legitimizes the difference in capacity, hierarchy and stratification.

Others speeches for industrial engineering education in Colombia

The questioning by rationality principles that have ruled industrial engineering until nowadays, the search of other principles and the vision of future for the discipline, in this Third group of peripheral elements is evidenced from the notion proposed by one of the professors, of <deindustrialization> (Figure 8). Which presents from its relationship with the socialization processes, both technology and knowledge itself, questioning Calvinist production processes, in which according to him, only interested is surplus value generation, ignoring the human being behind the machine, with creativity and with ability to transform technology, based on a very good knowledge of it, otherwise it ends up being enslaved by it, which is what is currently happening. In recent times, when the promotion of critical thinking in engineering education has taken on importance, from the understanding that engineering, ─moving at the intersection between the social and the technical─, should adapt technical knowledge to the economic, political and cultural contexts in which those are applied, that is, education in engineering should contemplate the study of the ideological conceptions that are behind the forms of power that motivate any implementation of engineering designs, the study of the actors involved, their interests and purposes and of the ways in which knowledge has been used to legitimize or delegitimize those interests or purposes. For which an analysis was advanced from various aspects of contemporary critical thinking, from the notions of technology and its transformation into power technology, in Foucault and other structuralism tendencies.

The proposition in this part of paper is deconstruction of industrialization notion or <deindustrialization>. For example, an industrial engineer who participates in the design and start-up of a plastic packaging manufacturing plant, since he does not have the tools for critical analysis of his work, he goes directly to execute what they demand without questioning the environmental effects and social causes of his work. The study plans, as shown by the (ECAES test, ICFES-ACOFI) mentioned above, do not provide the student with criteria to propose alternative models of production and consumption based on closed cycle processes or use value of goods.

As the currents of critical thinking in engineering education point out, ignoring whole series of both affective and cultural plots within the discourse, by completely, ─processes clearly observed in most interviews, especially in the younger agents interviewed─, entails to reduce the professor' work in industrial engineering to the simple reproduction of economistic linearity precepts ─typical of the field─, being able to conclude that field's agents Engineering and Operations Management Paris, France, July 26-27, 2018 © IEOM Society International persist and above all they insist on continuing reproducing and with new technologies, such as computer and informatics science, from cold and rigid principles of instrumental rationality that characterize the field since its emergence, and, in that sense, speaking of other discourses for the discipline is increasingly difficult.

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The serious danger involved in this problem of pretending to ignore the affective and social components present in all human activity within the discourse of industrial engineering professors, is nothing less than to underestimate the whole educational process, taking away its power of social identity construction and transformation ─characteristic in every educational process─, it means, reducing it to a simple production of robots.

Conclusions

With the configuration of the socialist bloc in world, after the second post-war period and the danger that for United States, as the nearest world power country, represented that this ideology was spread in Latin American countries, several studies and projects of cooperation and promotion to the industry were promoted. Education in technical and technological areas such as the Currie Study in 1951 "Bases of a promotion program for Colombia" and Atcon's basic plan on the Latin American university in 1961, favouring the emergence and demand of careers such as industrial engineering in the country. The emergence moment of education field in industrial engineering was marked by the influence of these reports.

With communism fall in the world in 1989, the interests of United States to contain its proliferation in the underdeveloped countries through the policies of protection to imports and boost local industry (Mission Currie and Alliance for Progress), were untimely changed by the (Washington Consensus) promulgated now by the total opening of these economies, towards a completely globalized international market, devastating almost completely the local industry and forcing the education sector to further diversify and self-manage; so that, industrial engineers who were previously trained to run large companies or act as employees in them, now, they become trained to act as small entrepreneurs or independent consultants in the new neoliberal paradigm of globalization. The teachers' speeches are also updated in the same way.

The central nucleus of industrial engineering professor's habitus is composed mainly of a high symbolic and abstract reality content, in what could be called a capacity for mathematical modelling, predictive and prescriptive, which is used to build their stories and which converts in social capital to perform in the field. This capacity for modelling leads him to perceive the world only from its commensurable dimension, always susceptible to being improved and standardized, reducing its possibilities for analysis and critical reflection.

Based on the interviews carried out, it is easily discernible how the teachers of the most recent generations give themselves more and more and without any reflection to the demands imposed on them by the university system to be able to stay in it, without opposing any resistance preventing it from arising a guild conscience and overshadowing any attempt at cohesion, each one works individually to meet academic standards, only meets with colleagues for the same purpose, is not interested in appropriating spaces for construction or deconstruction of the knowledge taught.

Older and retired teachers are those who have greater capacity for reflection about their work, however, there are no institutional mechanisms to be heard and taken into account their assessments and recommendations within the universities. There are stories that show, that it would be better in this moment of global crisis, to speak of deindustrialization, and to speak rather of a humanization of the processes.

The deindustrialization notion of productive processes and the return to more traditional modes of production, presented by one of the professors, where manual labour prevails and not mass production, is an interesting alternative for the deconstruction of developmental and globalization paradigms that characterize the current economic sector, which among others has relegated our economies to stop being producers to be outsourcing (our economy is concentrated in a precarious tertiary sector and in a high degree of informality of trade and services, because there is not industry). It is constituted in another fissure or point of break that could motivate new speeches for the professors of industrial engineering education field.

Figure 1 .

 1 Figure 1. The most frequent notions

Figure 4 .

 4 Figure 4. Notion of <engineering> The third central element, within this First group of elements, is the notion <make>, by the functional dimension

Figure 7 .

 7 Figure 7. Notion of < I >

Figure 8 .

 8 Figure 8. Notion of <deindustrialization>

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