Dissociation Reactions Research Articles

Dyotropic Rearrangement of an Iron-Aluminium Complex.

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well-defined Fe-Al dihydride complex with exogenous ligands (CO and CNR, R=Me, tBu, Xyl=2,6-Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in-depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IGMH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.

Reaction Dynamics of CO2 Hydrogenation on Iron Catalysts Using ReaxFF Molecular Dynamics Simulation.

The conversion of CO2 to hydrocarbons using catalysts is a promising route to utilize CO2 and produce more valuable chemicals in a sustainable manner. Recent studies have shown that iron-based catalysts perform well for the hydrogenation of CO2. While the hydrogenation reaction mechanism in the gas phase is straightforward, when catalyzed by iron it has been demonstrated to involve various chemical transformations, and the selectivity and conversion are strongly dependent on the particle size. To further investigate the dependence of the reactivity of iron catalysts on cluster size, we performed reactive molecular dynamics simulations using the ReaxFF force field (ReaxFF-MD) for iron nanoclusters of various sizes in a CO2 and H2-rich environment. We demonstrated that the homogeneous hydrogenation of CO2 was correctly described by this ReaxFF model. The dissociation mechanism of CO2 on the Fe4, Fe16 clusters, and the bcc(100) Fe slab agrees with previous DFT results. The ReaxFF-MD simulations suggest a strong dependence of reactivity on the cluster size, with the Fe4 cluster having the highest reactivity. We show that ReaxFF-MD provides a route to understand reaction mechanisms in these nonequilibrium reactive processes where fast processes and local minima are important.

Modeling and simulation of laser-ignited Al-PTFE reactive material in vacuum

Despite extensive investigations elucidating the initial response behavior of aluminized polytetrafluoroethylene (Al-PTFE) under atmospheric pressure, research on their response in lean-oxygen environments pertinent to propulsion and explosion scenarios is still lacking. This paper theoretically analyzes the multi-physical processes of laser-ignited Al-PTFE, identifying the initial response, main chemical reaction paths, and gas-phase product flow mechanisms. A dynamic reaction model of Al-PTFE considering material moving front, chemical reactions, gas-phase product dynamics, and variations in thermophysical properties, was developed. The robust coupling scheme in the model addresses nonlinear equations and fluid-solid coupling boundary conditions. Validation was achieved by comparing the ablation depth and plume number density field calculated by the model with the experimental results in the literature. The model reveals a positive correlation between laser fluence and both temperature growth rate and ablation depth of Al-PTFE, with the effects mainly observed in the full width at half maximum (FWHM) of the pulsed laser due to the thermal decomposition of the PTFE matrix. Simulations of the equilibrium constants and molar fractions of 19 components in the Al-PTFE ablation plume within the temperature range of 2000 K to 30,000 K at 0.001 Pa indicate that the equilibrium constants for dissociative reactions exceed those for ionization reactions, primarily in the early plume formation stages. Analysis of kinetic parameters and ambient pressure effects shows that during laser ablation, the maximum temperature of the plume initially appears near the ablation surface, shifting to the front, where the maximum velocity is always located. An elliptical shock wave forms due to adiabatic expansion of the plume, creating a cavity inside the plume. Lower ambient pressure increases plume expansion velocity, temperature, and size.

Spectroscopy and Photochemistry of [Al, N, C, O, H]: Connectivity to Aluminium-Bearing Species in the Universe.

Aluminium is one of the most abundant metals in the universe and impacts the evolution of various astrophysical environments. Currently detected Al-bearing molecules represent only a small fraction of the aluminium budget, suggesting that aluminium may reside in other species. AlO and AlOH molecules are abundant in the oxygen-rich supergiant stars such as VY Canis Majoris, a stellar molecular factory with 60+ molecules including the prebiotic NC-bearing species. Additional Al-bearing molecules with N, C, O, and H may form in O-rich environments with radiation-accelerated chemistry. Here, we present spectroscopic identification of novel aluminium-bearing molecules composed of [Al, N, C, O, H] and [Al, N, C, O] from the reactions of Al atoms and HNCO in solid argon matrix, which are potential Al-bearing molecules in space. Photoinduced transformations among six [Al, N, C, O, H] isomers and three [Al, N, C, O] isomers, along with their dissociation reactions forming the known interstellar species, have been disclosed. These results provide new insight into the chemical network of astronomically detected Al-bearing species in space.

High-Temperature Pyrolysis Study of 2-Methyl-2-butanol behind Reflected Shock Wave: Shock Tube and Computational Study.

Pyrolysis of a branched alcohol, 2-methyl-2-butanol (2M2BOH), was carried out behind the reflected shock wave in the temperature range of 1011-1303 K and under pressures varying from 9.3 to 14.6 atm. Qualitative and quantitative analysis of the postshock mixture was performed using gas chromatography-mass spectrometry and gas chromatography with a flame ionization detector, respectively. The rate coefficients for the C-C and C-O bond cleavage reaction pathways were calculated using the variational transition-state theory. The Rice-Ramsperger-Kessel-Marcus/Master equation was employed to calculate the rate coefficients for the H2O-elimination reactions, unimolecular dissociation, and isomerization reaction pathways. The overall decomposition rate coefficient for the 2-methyl 2-butanol (2M2BOH) was estimated to be , where activation energy is given in kcal mol-1. The reaction path analysis was performed, which gives information regarding the contribution of individual intermediate species toward the decomposition of 2M2BOH. A set of reactions was proposed and used to simulate the combustion chemistry of 2M2BOH, which consists of 48 reactions and 39 species. The experimentally measured and simulated mole fractions for the reactant and products showed reasonably good agreement. This work additionally investigates the effect of branching on the decomposition kinetics of long-chain alcohols.

Electronic modulation on allotropic Co2P/CoP heterojunctions with N, P co-doped porous carbon matrix through metal-injection toward high-efficiency water splitting

The interfacial electron modulation of electrocatalysts is a useful technique for promoting catalyst performance for the water-related dissociation reactions. Herein, a high-efficient Fe-doped allotropic Co2P/CoP heterojunction nanoparticles embedded in N, P co-doped carbon matrix was constructed. The intense electrical interfacial contacts between the allotropic heterojunction optimized the reaction kinetics by boosting efficient charged active centers, regulating the intermediate adsorption/desorption. The incorporation of Fe atoms further enhancing the heterointerface contact between CoP and Co2P by providing favorable electronic properties and special coordination environment, causing the interfacial coupling enhancement. Therefore, Fe-Co2P/CoP possesses outstanding performance in both hydrogen evolution reaction and oxygen evolution reaction, with small overpotentials of 174 mV and 286 mV at 10 mA·cm−2 in alkaline medium, respectively. And only 1.71 V battery voltage is needed for the Fe-Co2P/CoP (+, −) cell device with satisfactory durability. This finding provides valuable insights into the engineering of electronic structures of well-designed metal phosphides for water electrolysis.

Insights into the role of Mo in boosting CHx* oxidation for CO2 methane reforming

CHx* oxidation is one of the most vital routes to alleviate the carbon deposition problem of CO2 reforming of methane (DRM) reaction. Whereas, little experimental evidence has been observed on NiMo catalysts where the CHx* oxidation was dominant over its dissociation reaction. Herein, to experimentally unveil the CHx* oxidation route of NiMo catalysts, we design three catalysts with different particle sizes and structures. Among them, Mo/Niphy@SiO2 core shell catalyst demonstrated the dominant CHx* oxidation route over its dissociation based on in-situ diffuse reflectance infrared Fourier transform spectroscopy experiments. This was attributed to the confinement effect of SiO2 and the formation of Ni–Mo alloy, inhibiting the CHx* dissociation reaction. It exhibited relatively stable CH4 and CO2 conversions (77 % and 75 % respectively) within 180 h. By contrast, on Mo/Niphy catalyst which has a big Ni size, CHx* was mainly dissociated to C* and oxidized to CO which further underwent a disproportion reaction to produce CO2 and C*, leading to the severe carbon deposition and unstable DRM performance. The strategy to unveil the dominant role of CHx* oxidation via design catalysts with different sizes and structures sheds light on the study of reaction mechanism of other reactions.

Ion association behaviors in the initial stage of calcium carbonate formation: An ab initio study

In this work, we performed static density functional theory calculations and ab initio metadynamics simulations to systematically investigate the association mechanisms and dynamic structures of four kinds of ion pairs that could be formed before the nucleation of CaCO3. For Ca2+–HCO3− and Ca2+–CO32− pairs, the arrangement of ligands around Ca2+ evolves between the six-coordinated octahedral structure and the seven-coordinated pentagonal bipyramidal structure. The formation of ion pairs follows an associative ligand substitution mechanism. Compared with HCO3−, CO32− exhibits a stronger affinity to Ca2+, leading to the formation of a more stable precursor phase in the prenucleation stage, which promotes the subsequent CaCO3 nucleation. In alkaline environments, excessive OH− ions decrease the coordination preference of Ca2+. In this case, the formation of Ca(OH)+–CO32− and Ca(OH)2–CO32− pairs favors the dissociative ligand substitution mechanism. The inhibiting effects of OH− ion on the CaCO3 association can be interpreted from two aspects, i.e., (1) OH− neutralizes positive charges on Ca2+, decreases the electrostatic interactions between Ca2+ and CO32−, and thus hinders the formation of the CaCO3 monomer, and (2) OH− decreases the capacity of Ca2+ for accommodating O, making it easier to separate Ca2+ and CO32− ions. Our findings on the ion association behaviors in the initial stage of CaCO3 formation not only help scientists evaluate the impact of ocean acidification on biomineralization but also provide theoretical support for the discovery and development of more effective approaches to manage undesirable scaling issues.

Kinetic insights into ammonia-hydrogen doped ignition and emission assisted by nanosecond pulsed discharge

Non-equilibrium plasma is applied for the first time to ignite the ammonium-hydrogen mixture and reduce the NOx/N2O emission with effect in this work. Gas chromatography (GC) experiments as well as a detailed kinetic model, including neutral molecules, free radicals, charged particles, vibratory excited states, and electron excited states, are integrated to investigate the kinetic process of ammonia-hydrogen doped ignition and NOx/N2O emission facilitated by nanosecond pulsed discharge. The numerical model closely matches the GC-measured values of NH3 consumption, H2 increase, and N2O production. Pathway fluxes of important species and sensitivity analysis of ignition delay time reveal that the addition of non-equilibrium plasma has an obvious promotion effect on ammonia and hydrogen-doped oxidation and ignition. The initial ignition temperature significantly impacts the ignition delay time, with a more pronounced plasma-promotion effect observed at lower temperatures. Conversely, as the hydrogen mixing ratio increases, the ignition delay time decreases, yet the generation of NO and N2O increases. This is attributed to the heightened production of H and NH through elementary reactions such as NH3+HNH2+ H2, H + O2O + OH, and OH + H2H + H2O. Nevertheless, NO and N2O emissions are reduced by 1-2 orders of magnitude with plasma assistance compared to auto-ignition. The reduction in NO emissions can be attributed to increased consumption in the pathway of NO + NH2N2 + H2O and decreased formation in the pathways of HNO + O2HO2 + NO and NH + NON2O + H. Additionally, it was discovered that the electron attachment dissociation reaction e + N2O → O− + N2 predominantly contributes to the reduction of N2O. These research findings significantly contribute to advancing our understanding of the kinetics involved in ammonia-hydrogen doped ignition and emissions, particularly with plasma assistance, for potential engine applications.

The Role and Lifetime of Dissociative Heterogeneous Processes in Improving Simulated Ozone on Mars

AbstractOzone simulated in Mars Global Climate Models (MGCMs) is used to assess the underlying chemistry occurring in the atmosphere. Currently, ozone total column abundance (TCA) is under‐predicted in MGCMs by up to 120%, implying missing or inaccurate chemistry in models. Heterogeneous reactions of hydroxyl radicals (HOX) have been offered as an explanation for some of this bias, because they cause ozone to increase at locations where it's currently under‐predicted. We use four simulations to compare modeled ozone TCA with observations from the UVIS spectrometer aboard the ExoMars Trace Gas Orbiter to improve the representation of heterogeneous processes and their impact on ozone. We use a gas‐phase only run, a dissociative scheme, an adsorbed HOX retention scheme, and a hybrid scheme that combines the dissociative mechanism with the retention of HOX on water ice. We find retention of HOX is dependent on water ice sublimation, and ozone abundance increases when water ice persists for longer periods (1–20 sols). Over time, the loss of HOX causes a depletion in H2O2 concentration (HOX reservoir), and thus allows ozone concentration to increase. When adsorbed HOX are desorbed and dissociate into other by‐products, HOX are not immediately available to destroy ozone. This results in larger ozone concentrations than if desorbed HOX are released directly back into their gaseous states. When using the hybrid scheme, ozone TCA is increased up to 50% where the ozone deficit is greatest, demonstrating the best agreement with observations, and implying that HOX radicals are both retained when adsorbed and dissociate.

Unraveling the Photodissociation Branching and Pathways of Methane at 118 nm by Imaging the CH3, CH2, and CH Fragments.

Under irradiation of a vacuum ultraviolet (VUV) photon, methane dissociates and yields multiple fragments. This photochemical behavior is not only of fundamental importance but also with wide-ranging implications in several branches of science. Despite that and numerous previous investigations, the product channel branching is still under debate, and the underlying dissociation mechanisms remain elusive. In this study, the photofragment imaging technique was exploited for the first time to map out the momentum and anisotropy parameter distributions of the CH3, CH2, and CH fragments at the 118 nm photolysis wavelength (10.48 eV photon energy). In conjunction with previously reported results of the H atom fragment at 121.6 nm (10.2 eV), a complete set of product channel branching in both two-body and three-body fragmentations is accurately determined. We concluded that extensive nonadiabatic transitions partake in the processes with two-body fragmentations accounting for more than 90% of overall photodissociation, for which the channel branching values for CH2 + H2 and CH3 + H are about 0.66 and 0.25, respectively. Careful kinematic analysis enables us to untangle the intertwined triple fragmentations into the CH2(X̃ 3B1 and ã 1A1) + H + H and CH(X2Π) + H + H2 channels and to evidence their underlying sequential (or stepwise) mechanisms. With the aid of electronic correlation and prior theoretical calculations of the potential energy surfaces, the most probable or dominant dissociation pathways are elucidated. Comparisons with fragmentary reports in the literature on various photochemical aspects are also documented, and discrepancies are clarified. This comprehensive study benchmarks the VUV photochemistry of methane and advances our understanding of this important process.

Binding Affinity Determination in Drug Design: Insights from Lock and Key, Induced Fit, Conformational Selection, and Inhibitor Trapping Models.

Binding affinity is a fundamental parameter in drug design, describing the strength of the interaction between a molecule and its target protein. Accurately predicting binding affinity is crucial for the rapid development of novel therapeutics, the prioritization of promising candidates, and the optimization of their properties through rational design strategies. Binding affinity is determined by the mechanism of recognition between proteins and ligands. Various models, including the lock and key, induced fit, and conformational selection, have been proposed to explain this recognition process. However, current computational strategies to predict binding affinity, which are based on these models, have yet to produce satisfactory results. This article explores the connection between binding affinity and these protein-ligand interaction models, highlighting that they offer an incomplete picture of the mechanism governing binding affinity. Specifically, current models primarily center on the binding of the ligand and do not address its dissociation. In this context, the concept of ligand trapping is introduced, which models the mechanisms of dissociation. When combined with the current models, this concept can provide a unified theoretical framework that may allow for the accurate determination of the ligands' binding affinity.

Determining the influence of relative humidity on the working parameters of a gas sensor based on zinc oxide

This paper investigates the dependence of operating parameters of a gas sensor based on zinc oxide obtained by the method of direct current magnetron sputtering. The production of gas sensor films was carried out using a VUP-5M vacuum unit with an original material-saving magnetron. The study of the dependence of the working parameters of the gas sensor was carried out under standard conditions. It was found that with increasing humidity, the electrical resistance of the gas sensor decreases and, accordingly, the sensitivity to the target gas decreases. A significant reaction of the gas sensor to an increase in humidity was observed in the range of 65–80 % relative humidity. The mechanism of influence of relative humidity on the sensitivity of a gas sensor based on ZnO was investigated. The change in resistance of the gas sensor is caused by trapped electrons on adsorbed oxygen molecules on the surface of the sensitive layer. The capture of electrons from the conduction zone leads to bending of the conduction zone and an increase in the space charge zone, respectively, to a change in the resistance of the sensitive layer of the gas sensor. In the atmosphere, when O2 molecules are adsorbed on the ZnO surface, they remove an electron from the conduction band. The reaction of oxygen adsorbed on the ZnO surface with reducing gases and the replacement of adsorbed oxygen with other molecules changes the bending of the conduction band and reduces the area of space charge. Adsorption of water on the surface of zinc oxide occurs according to the dissociation mechanism, which consists in the adsorption of steam molecules or hydroxyl groups with the subsequent displacement of previously adsorbed oxygen and free electrons and, accordingly, leads to a decrease in the sensitivity of the gas sensor. In addition, the adsorption of water vapor (H2O) molecules leads to less chemisorption of oxygen species on the ZnO surface due to the reduction of the surface area, which is responsible for the sensor response. Approaches to reduce the influence of relative humidity on the sensitivity of a gas sensor based on zinc oxide have been proposed

Characterization and identification of major flavonoids of bamboo leaf extract by HPLC/ESI-QTOF-MS/MS

Bamboo leaf extract (BLE) is a pale brown powder extracted from bamboo leaves, and it is listed in the Chinese Standard GB-2760 as a legal and safe food additive. The present study aims to identify and characterize the major flavonoids in BLE. The identification of major flavonoids was carried out using ultra performance liquid chromatography combined with electrospray ionization quadruple time-of-flight tandem mass spectrometry (HPLC/ESI-QTOF-MS/MS). A total of 31 flavonoid compounds were identified and tentatively characterized base on reference standards and MS dissociation mechanisms. HPLC/ESI-QTOF-MS can serve as an important analytical platform to identification structure of bamboo leaf flavonoids (BLF).

Mobility-Assisted Pseudo-MS3 Sequencing of Protein Ions.

The sequencing of intact proteins within a mass spectrometer has many benefits but is frequently limited by the fact that tandem mass spectrometry (MS/MS) techniques often generate poor sequence coverages when applied to protein ions. To overcome this limitation, exotic MS/MS techniques that rely on lasers and radical chemistry have been developed. These techniques generate high sequence coverages, but they require specialized instrumentation, create products through multiple dissociation mechanisms, and often require long acquisition times. Recently, we demonstrated that protein ions can be dissociated in a trapped ion mobility spectrometry (TIMS) device prior to mobility separation in a commercial timsTOF. All generated product ions were distributed throughout the mobility dimension, and this separation enabled deconvolution of complex tandem mass spectra and could enable facile pseudo-MS3 interrogation of generated product ions with the downstream quadrupole and collision cell. A second activation step improves sequence coverage because the most labile bonds have been depleted during the first dissociation and subsequent dissociation events are more evenly distributed throughout the product ion backbone. In this work, we explore the potential of this mobility-assisted pseudo-MS3 (MAP) method on a commercial timsTOF and timsTOF Pro 2. We demonstrate that while MAP only generates 92% of the sequence coverage of the most effective MS/MS technique, it accomplished this feat in 1.5 min and could be facilely integrated with liquid chromatographic separations.

Ab initio study of the adsorption of O, O2, H2O and H2O2 on UO2 surfaces using DFT+U and non-collinear magnetism

In order to model correctly the corrosion of spent nuclear fuel under disposal conditions, it is important to understand its behavior in the presence of oxidants. To advance in this direction, we consider the oxidation of UO2. We investigate computationally the adsorption of various species on its three most stable surfaces: (111), (110), and (100), with emphasis on incorporating a full non-collinear PBE+U approach. Various species, namely O, O2, H2O and H2O2 are considered due to their relevance for the oxidation of UO2. The dissociation energy and an estimate for the dissociation barrier for O2 were obtained, using the preferred adsorption configurations of O and O2. The adsorption configurations for H2O in our study compare well with previous studies that used collinear approximations, both in terms of relative stability of configurations and bond lengths. Differences in adsorption energies were found, which may be important for reaction kinetics. Dissociative reactions in which the water molecule splits in hydrogen and hydroxyl occur only on one of the three surfaces. The hydrogen further reacts with a surface oxygen to also form a hydroxyl group. Not surprisingly, we find that H2O2 binds more strongly to the three surfaces than water (lower formation energy), and similar to H2O adsorption, dissociative reactions may occur. The dissociated hydrogen reacts with a surface oxygen to form a hydroxyl group and the hydroperoxyl molecule binds with a surface uranium. Our study, which includes a detailed study of electron transfer, magnetic structure and the preferred adsorption configurations, gives insight into the uranium oxidation states and the influence of surface geometry on adsorption. The findings contribute to a more comprehensive understanding of the early stages of UO2 oxidation.

Numerical Investigation of the Reactive Impinging Jet Cooling – the role of vortices in heat and mass transfer intensification

While fundamental mechanisms of non-reactive jet impingement have been extensively researched, the reactive jet impingement is yet unexplored although it offers the potential to increase further the heat transfer. The present work fills this knowledge gap via high-fidelity numerical simulation of reactive jet impingement invoking the finite rate one-step chemistry. Endo-/exothermic reactions are found to have very limited influence on time-averaged fluid flow, while they induce substantial modifications in heat transfer characteristics. This influence is manifested as discernible changes in the momentary or instantaneous fluid dynamics. Specifically, the primary vortices are responsible for downwashing cold fluid (mostly N2O4) towards the hot plate, posing low local convective heat transfer. The secondary vortices are responsible for extracting heat from the hot plate via the dissociation reaction N2O4→2NO2, followed by transporting NO2 away from the hot plate and towards the upwashing side of the primary vortex. At the upside of the primary vortex, hot NO2 is cooled by the environment, therefore reforming N2O4 to give out energy. This intense and long-lasting heat absorption and heat release process explains the outstanding performance of reactive jet impingement.

Evidence of phenotypes and dissociative diagnostic markers for demonic possession syndrome

ObjectiveAccording to clinical models of personality, patients with dissociative identity disorder (DID) who have experienced demonic possession (psychiatric possession syndrome or PPS) may present two profiles: the schizo-paranoid profile (characteristic of psychotic spectrum disorder or PSD) and the hysteroid-histrionic profile (characteristic of affective disorders). The present study aimed to examine the clinical and statistical evidence of these phenotypic personality structures in patients with PPS and DID (with and without PSD). MethodsThe design of this investigation was based on structural equation modeling. A total of 303 patients were diagnosed with DID without psychosis and 306 were diagnosed with DID with PSD; the diagnosis was made by clinical professionals who collaborated on this research and conducted the assessment tests. All patients completed clinical questionnaires on their personality structures, and dissociation level was also measured. The physician-psychiatrist assessed each patient using the Psychiatric Possession Syndrome Checklist (PPS-C), a new hetero-applied questionnaire on the symptomatic intensity of PPS. ResultsThe results led to the conclusion that both personality structures were 65 %–66 % predictive of possession syndrome. Dissociative symptoms attributable to DID modulated the PPS variance by 21 % to 26 %. Validity evidence has been obtained for the combined phenotypic personality model that integrates DID and PSD structures. ConclusionsWe discuss the psychopathological and therapeutic implications of the analysis on the dissociative mechanisms involved in each personality phenotype. We also provide a graphical summary of the PPS symptoms, organized into a normalized distribution, which may prove useful for professional practice. Additionally, we present potential clinical scores from the PPS-C.

Investigating electron-induced dissociation dynamics in the organometallic precursor Fe(CO)5: a nonadiabatic molecular dynamics approach

This research employs excited states molecular dynamics simulations to explore the electron-induced dissociation behavior of Fe(CO)5 molecules, with the specific focus on electronic excitation. The study initiates with the detailed analysis of the molecule’s stable ground state structure. Subsequent simulations reveal distinctive dissociation patterns in various bonds, particularly noting the rapid dissociation of bonds between Fe and C1, Fe and C2, while those with Fe and C3 oscillate without complete dissociation. Emphasizing the influence of the transition from the highest occupied molecular orbital to the lowest unoccupied molecular orbital on reactivity, the investigation sheds light on the charge transfer phenomenon during dissociation through Bader analysis. Insights into transitions between excited and ground states are derived from the time evolution of the Kohn–Sham orbital. This study significantly contributes to understanding intricate dissociation mechanisms under electronic excitation, especially in molecules like Fe(CO)5 characterized by complex chemical bonds. Beyond theoretical exploration, the research holds practical significance for applications in nanomaterials, such as focused electron beam-induced deposition and the fabrication of nanoscale structures, enriching our comprehension of electronic-excitation-induced dissociation and advancing both theoretical understanding and practical applications in this field.

Kinetic Isotope Effects and the Mechanism of CO2 Insertion into the Metal-Hydride Bond of fac-(bpy)Re(CO)3H.

The 1,2-insertion reaction of CO2 into metal-hydride bonds of d6-octahedral complexes to give κ1-O-metal-formate products is the key step in various CO2 reduction schemes and as a result has attracted extensive mechanistic investigations. For many octahedral catalysts, CO2 insertion follows an associative mechanism in which CO2 interacts directly with the coordinated hydride ligand instead of the more classical dissociative mechanism that opens an empty coordination site to bind the substrate to the metal prior to a hydride migration step. To better understand the associative mechanism, we conducted a systematic quantum chemical investigation on the reaction between CO2 and fac-(bpy)Re(CO)3H (1-Re-H; bpy = 2,2'-bipyridine) starting with the gas phase and then moving to THF and other solvents with increased dielectric constants. Detailed analyses of the potential energy surfaces (PESs) and intrinsic reaction coordinates (IRCs) reveal that the reaction is enabled in all media by an initial stage of making a 3c-2e bond between the carbon of CO2 and the metal-hydride bond that is most consistent with an organometallic bridging hydride Re-H-CO2 species. Once CO2 is bent and anchored to the metal-hydride bond, the reaction proceeds by a rotation motion via a cyclic transition state TS2 that interchanges Re-H-CO2 and Re-O-CHO coordination. The combined stages provide an asynchronous-concerted pathway for CO2 insertion on the Gibbs free energy surface with TS2 as the highest energy point. Consideration of TS2 as a rate-determining TS gives activation barriers, inverse KIEs, substituent effects, and solvent effects that agree with the experimental data available in this system. An important new insight revealed by the analyses of the results is that the initial stage of the reaction is not a hydride transfer step as has been assumed in some studies. In fact, the loose vibration of the TS that can be identified for the first stage of the reaction in solution (TS1) does not involve the Re-H stretching vibrational mode. Accordingly, the imaginary frequency of TS1 is insensitive to deuteration, and therefore, TS1 leads to no significant KIE.