Singlet Potential Energy Surfaces Research Articles

Theoretical investigations on the atmospheric reaction of n-C3H7O2 with ClO radicals

As a key intermediate during propane oxidation, n-propyl peroxy radicals (n-C3H7O2) play significant roles in the atmosphere. In this study the reaction of n-C3H7O2 with chlorine monoxide ClO was studied using quantum chemistry methods. Result shows that addition–elimination, substitution and abstraction mechanisms were located on the singlet and triplet potential energy surfaces (PESs). On the singlet PES, the final products of C2H5CHO + HClO2 and C2H5CHOO + HOCl will be feasible with low or moderate barriers. While on the triplet PES all barriers are too high and can be negligible to the overall reaction. Moreover, it is presumed that the title reaction might be potential source of C2H5CHOO in the atmosphere, especially in the marine boundary layer (MBL) with high ClO concentrations.

Kinetic Study and Reaction Mechanism of the Gas-Phase Thermolysis Reaction of Methyl Derivatives of 1,2,4,5-Tetroxane.

Tetroxane derivatives are interesting drugs for antileishmaniasis and antimalaric treatments. The gas-phase thermal decomposition of 3,6,-dimethyl-1,2,4,5-tetroxane (DMT) and 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (acetone diperoxide (ACDP)) was studied at 493-543 K by direct gas chromatography by means of a flow reactor. The reaction is produced in the injector chamber at different temperatures. The resulting kinetics Arrhenius equations were calculated for both tetroxanes. Including the parent compound of the series 1,2,4,5-tetroxane (formaldehyde diperoxide (FDP)), the activation energy and frequency factors decrease linearly with the number of methyl groups. The reaction mechanisms of ACDP and 3,6,6-trimethyl-1,2,4,5-tetroxane (TMT) decomposition have been studied by means of the DFT method with the BHANDHLYP functional. Our calculations confirm that the concerted mechanism should be discarded and that only the stepwise mechanism occurs. The critical points of the singlet and triplet state potential energy surfaces (S- and T-PES) of the thermolysis reaction of both compounds have been determined. The calculated activation energies of the different steps vary linearly with the number of methyl groups of the methyl-tetroxanes series. The mechanism for the S-PES leads to a diradical O···O open structure, which leads to a C···O dissociation in the second step and the production of the first acetaldehyde/acetone molecule. This last one yields a second C···O dissociation, producing O2 and another acetone/acetaldehyde molecule. The O2 molecule is in the singlet state. A quasi-parallel mechanism for the T-PES from the open diradical to products is also found. Most of the critical points of both PES are linear with the number of methyl groups. Reaction in the triplet state is much more exothermic than the singlet state mechanism. Transitions from the singlet ground state, S0 and low-lying singlet states S1-3, to the low-lying triplet excited states, T1-4, (chemical excitation) in the family of methyl tetroxanes are also studied at the CASSCF/CASPT2 level. Two possible mechanisms are possible here: (i) from S0 to T3 by strong spin orbit coupling (SOC) and subsequent fast internal conversion to the excited T1 state and (ii) from S0 to S2 from internal conversion and subsequent S2 to T1 by SOC. From these experimental and theoretical results, the additivity effect of the methyl groups in the thermolysis reaction of the methyl tetroxane derivatives is clearly highlighted. This information will have a great impact for controlling these processes in the laboratory and chemical industries.

Photoisomerization of (Cyanomethylene)cyclopropane (C5H5N) to 1-Cyano-2-methylenecyclopropane in an Argon Matrix.

Broad-band ultraviolet photolysis (λ > 200 nm) of (cyanomethylene)cyclopropane (5) in an argon matrix at 20 K generates 1-cyano-2-methylenecyclopropane (7), a previously unknown compound. This product was initially identified by comparison of its infrared spectrum to that predicted by an anharmonic MP2/6-311+G(2d,p) calculation. This assignment was unambiguously confirmed by the synthesis of 1-cyano-2-methylenecyclopropane (7) and observation of its authentic infrared spectrum, which proved identical to that of the observed photoproduct. We investigated the singlet and triplet potential energy surfaces associated with this isomerization process using density functional theory and multireference calculations. The observed rearrangement of compound 5 to compound 7 is computed to be endothermic (3.3 kcal/mol). We were unable to observe the reverse reaction (7 → 5) under the photochemical conditions.

Study on Formation of Interstellar C7H from Reactions C4 + C3H2 and C4H + C3H.

We interrogated C7H produced from reactions C4 + C3H2/C4H + C3H → C7H + H using both translational and photoionization spectroscopy. Reactants C3H, C3H2, C4, and C4H were synthesized in two crossed beams of 1% C2H2/He ignited by pulsed high-voltage discharge. The individual contributions of reactions C4 + C3H2 and C4H + C3H to product C7H were evaluated as 17:83 from reactant concentrations in both molecular beams. The translational energy distribution, the angular distribution, and the photoionization efficiency curve of product C7H were unraveled. C7H was identified as the most stable linear isomer by its photoionization efficiency curve that features two ionization thresholds corresponding to separate transitions to singlet and triplet states of l-C7H+. The quantum-chemical calculations indicate that the associations of C4 with C3H2 and C4H with C3H incur no entrance barriers, and the most favorable exit channel leads to product l-C7H + H. It is the first time demonstrating that C7H is producible from reactions 1,3C4 + 1C3H2 and 2C4H + 2C3H on the lowest-lying singlet and triplet potential energy surfaces of 1,3C7H2. This work implies that the reactions of C4 + C3H2 and C4H + C3H might have contributions to interstellar C7H to some extent as compared with the C + C6H2 reaction commonly adopted in an astrochemical model.

Insight into the reactions of n-, iso-, sec- and tert-Butylperoxy radicals with hydroperoxyl radical in the Atmosphere: Reaction Mechanism, thermodynamic analysis and kinetics

Butylperoxy radical (C4H9O2) is recognized today as an important atmospheric intermediate which formed by the oxidation of butane (C4H10), playing a crucial role in the cycling of carbon. This work gives a theoretical investigation of the reaction mechanism, thermodynamic analysis and kinetics of the reactions between HO2 and four isomers (n-, iso-, sec- and tert-Butylperoxy radicals) of C4H9O2, which has been computed using the CCSD(T)/aug-cc-pVDZ//B3LYP/6-311G(d,p) level of theory. As a result, the above four reactions proceed on both singlet and triplet potential energy surfaces have been demonstrated. Additionally, the formation of alkylhydroperoxides and 3O2via triplet hydrogen abstraction from the four reactions are the major reaction channels while other singlet product channels are negligibly small. Besides, rate coefficients for the title reactions were estimated using the transition state theory (TST) over the temperature range 258 – 378 K, and these results exhibit a negative temperature dependence.

Unusual Spin States in Noble Gas Inserted Noble Metal Halocarbenes, FNgCM (Ng = Kr, Xe, Rn; M = Cu, Ag, Au).

Recent experimental detection of noble gas (Ng) inserted fluorocarbenes, viz., FKrCF and FXeCF, which were theoretically predicted by our group earlier and very recent experimental evidences on gold-halogen analogy motivated us to explore the possibility of the existence of noble gas inserted noble metal fluorocarbene, FNgCM (Ng = Kr, Xe, and Rn; M = Cu, Ag, and Au) molecules. Ab initio quantum chemical calculations have been performed to investigate structure, stability, vibrational frequency, charge distribution and bonding analysis of FNgCM molecules by employing DFT, MP2, and CCSD(T) methods. For the purpose of comparison FNgCH molecules have also been studied. One of the important outcomes of the study is that the predicted FNgCH, FNgCCu and FNgCAg molecules are more stable in their triplet electronic states, whereas the FNgCAu molecules are found to be more stable in their singlet potential energy surface, similar to the recently observed FNgCF (Ng = Kr and Xe) molecules, although the singlet state is the lowest energy state for all the precursor carbene molecules. The gold atom behaves as a better electron donor due to the pronounced relativistic effect as compared to hydrogen, copper and silver atoms, resulting in stabilization of the singlet carbene molecule indicating halogen like chemical behavior of gold. These molecules are found to be thermodynamically stable with respect to all plausible 2-body and 3-body dissociation channels, except the one that leads to the formation of the global minimum products. However, metastable nature of the predicted molecules has been proved by studying the saddle point corresponding to the transition from the minima to the global minimum products. Sufficient barrier heights provide the kinetic stability to the predicted FNgCM molecules, which prevent them from dissociating into their respective global minimum products. All the results clearly indicate that the F-Ng bond is mostly ionic in nature with certain amount of covalent character while Ng-C bond is found to be covalent in nature. Furthermore, atoms-in-molecule (AIM), energy decomposition analysis (EDA) and charge distribution analyses suggest that the predicted FNgCM molecules essentially exist in the form of [F]δ-[NgCM]δ+. The calculated results also indicate that it may be possible to prepare and characterize the predicted molecules by suitable experimental technique(s).

Four-body singlet potential-energy surface for reactions of calcium monofluoride

A full six-dimensional Born-Oppenheimer singlet potential-energy surface is constructed for the reaction CaF $+$ CaF $\ensuremath{\rightarrow}\phantom{\rule{4pt}{0ex}}{\mathrm{CaF}}_{2} +$ Ca using a multireference configuration-interaction electronic structure calculation. The ab initio data thus calculated are interpolated by Gaussian process regression. The four-body potential-energy surface features one ${D}_{2h}$ global minimum and one ${C}_{s}$ local minimum, connected by a barrierless transition state that lends insight to the reaction mechanism. This surface is intended to be of use in understanding ultracold chemistry of CaF molecules.

Proton Reaction Path in Base Pairs of DNA Molecule According to the Complete Active Space Self-Consistent Field Method

The double proton transfer reaction paths in AT and CG base pairs of DNA molecule are calculated in the Complete Active Space Self-Consistent Field method and compared with the same paths in Density Functional Theory with B3LYP approximation approach. We found that an essential increase of an activation energy, which significantly reduces the probability of spontaneous mutations in DNA via double proton transfer. There exist two transition points on the singlet potential energy surface divided by a flat region for GC base pair. The applicability of various quantum-chemical methods for description of double proton transfer reactions was discussed.

Artificial Neural Network-Derived Unified Six-Dimensional Potential Energy Surface for Tetra Atomic Isomers of the Biogenic [H, C, N, O] System.

Recognition of different structural patterns in different potential energy surface regions, such as in isomerizing quasilinear tetra atomic molecules, is important for understanding the details of underlying physics and chemistry. In this respect, using three variants of artificial neural networks (ANNs), we investigated the six-dimensional (6-D) singlet potential energy surfaces (PES) of tetra atomic isomers of the biogenic [H, C, N, O] system. At first, we constructed a separate ANN potential for each of the studied isomers. In the next step, a comparative assessment of the separate ANN models led to the setting up of a unified 6-D singlet PES equally and accurately describing all studied isomers. The constructed unified model yields relative energies comparable to those obtained either from the gold standard CCSD(T) method or from separate ANNs for each of the studied isomers. The accuracy of the unified singlet PES is on the order of 10-4 Hartrees (0.1 kcal/mol). The developed PES in this work captures the main features of nonlinear and quasilinear tetra atomic isomers of this biogenic system.

Theoretical studies on the reaction mechanisms of the oxidation of tetramethylethylene using MO3Cl (M=Mn, Tc and Re)

A theoretical study on the reaction mechanisms of the addition of transition metal oxo complexes of the type MO3Cl (M = Mn, Tc, and Re) to tetramethylethylene (TME) is presented. Theoretical calculations using B3LYP/LACVP* and M06/LACVP* (LACVP* is a combination of the 6-31G(d) basis set along with LANL2DZ pseudopotentials on the metallic centres) were performed and the results are discussed within the framework of reaction energetics. The nature of the stability of the reaction mechanisms was equivalent for both theories. However, the M06/LACVP* simulations generally had slightly lower energies and shorter bond lengths compared to the B3LYP/LACVP* computations.Furthermore, it was observed that the reaction does not proceed via the stepwise reaction mechanism due to kinetic and thermodynamic instabilities. Epoxidation was also found to occur via the [2 + 2] concerted reaction mechanism for the MO3Cl (M = Tc and Re) whereas the permanganyl chloride complex epoxidizes TME via the [2 + 1] concerted reaction mechanism on the singlet potential energy surface (PES). Dioxylation was observed to proceed via the [3 + 2] route for the addition of MO3Cl (M = Tc and Re) and TME. Results indicate that all reaction surfaces were unselective except for the permanganyl chloride catalyzed surface which leads to the formation of epoxides exclusively.Changes in temperatures from 298.15 K to 373.15 K, resulted in kinetically and thermodynamically unstable reaction pathways as the activation and reaction energies increased generally. On the singlet PES, the rate constant calculations showed that the [3 + 2] catalyzed surface reaction mechanism leading to dioxylation was faster than the [2 + 2] mechanism in cases where plausible.Theoretical values from the global reactivity parameters, namely the chemical hardness, chemical potential, electrophilic and nucleophilic indices, are in good correlation with the DFT activation and reaction energies at both levels of theories. Thus, as the electrophilic nature of the metal decreases from Mn to Re, so do the activation and reaction energies increase from Mn to Re, indicating that the higher the electrophilicity of the metal centre, the more spontaneous the oxidation reaction.

Reactions O(3P, 1D) + HCCCN(X1Σ+) (Cyanoacetylene): Crossed-Beam and Theoretical Studies and Implications for the Chemistry of Extraterrestrial Environments.

Cyanoacetylene (HCCCN), the first member of the cyanopolyyne family (HCnN, where n = 3, 5, 7, ...), is of particular interest in astrochemistry being ubiquitous in space (molecular clouds, solar-type protostars, protoplanetary disks, circumstellar envelopes, and external galaxies) and also relatively abundant. It is also abundant in the upper atmosphere of Titan and comets. Since oxygen is the third most abundant element in space, after hydrogen and helium, the reaction O + HCCCN can be of relevance in the chemistry of extraterrestrial environments. Despite that, scarce information exists not only on the reactions of oxygen atoms with cyanoacetylene but with nitriles in general. Here, we report on a combined experimental and theoretical investigation of the reactions of cyanoacetylene with both ground 3P and excited 1D atomic oxygen and provide detailed information on the primary reaction products, their branching fractions (BFs), and the overall reaction mechanisms. More specifically, the reactions of O(3P, 1D) with HCCCN(X1Σ+) have been investigated under single-collision conditions by the crossed molecular beams scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy, Ec, of 31.1 kJ/mol. From product angular and time-of-flight distributions, we have identified the primary reaction products and determined their branching fractions (BFs). Theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) were performed to assist the interpretation of the experimental results and clarify the reaction mechanism. Adiabatic statistical calculations of product BFs for the decomposition of the main triplet and singlet intermediates have also been carried out. Merging together the experimental and theoretical results, we conclude that the O(3P) reaction is characterized by a minor adiabatic channel leading to OCCCN (cyanoketyl) + H (experimental BF = 0.10 ± 0.05), while the dominant channel (BF = 0.90 ± 0.05) occurs via intersystem crossing to the underlying singlet PES and leads to formation of 1HCCN (cyanomethylene) + CO. The O(1D) reaction is characterized by the same two channels, with the relative CO/H yield being slightly larger. Considering the recorded reactive signal and the calculated entrance barrier, we estimate that the rate coefficient for reaction O(3P) + HC3N at 300 K is in the 10-12 cm3 molec-1 s-1 range. Our results are expected to be useful to improve astrochemical and photochemical models. In addition, they are also relevant in combustion chemistry, because the thermal decomposition of pyrrolic and pyridinic structures present in fuel-bound nitrogen generates many nitrogen-bearing compounds, including cyanoacetylene.

Computational Study of Iron-Catalyzed Intramolecular [2 + 2] Cycloaddition and Cycloisomerization of Enyne Acetates: Mechanism and Selectivity

The mechanism of iron-catalyzed intramolecular [2 + 2] cycloaddition and cycloisomerization of enyne acetates has been investigated with DFT computations. Both mechanisms start the catalytic cycle from the stepwise 1,2-acyloxy migration to afford the iron carbene. The [2 + 2] cycloaddition mechanism involves subsequent key steps of [2 + 2] cycloaddition, 1,2-acyloxy migration, and reductive elimination to generate the azabicyclo [3.2.0] heptane product, with the reductive elimination being the rate-determining step. The cycloisomerization mechanism involves subsequent key steps of [2 + 2] cycloaddition, stepwise 1,4-acyloxy migration to produce the allenylpyrrolidine product, with the 1,4-acyloxy migration being the rate-determining step. Reaction potential energy surfaces for two model substrates that have or do not have alkene-terminal substituents have been investigated and the origins of the selectivities have been disclosed. Moreover, energy profiles with three possible spin states (SFe = 0, 1, 2) have been considered. The reaction is suggested to occur mainly on the singlet potential energy surface with a few spin crossovers between singlet and triplet states involved, which indicates that this reaction should have two-state reactivity (TSR).

A combined crossed molecular beam and theorerical study of the O(3P,1D) + acrylonitrile (CH2CHCN) reactions and implications for combustion and extraterrestrial environments.

Acrylonitrile (CH2CHCN) is ubiquitous in space (molecular clouds, solar-type star forming regions, and circumstellar envelopes) and is also abundant in the upper atmosphere of Titan. The reaction O(3P) + CH2CHCN can be of relevance in the chemistry of the interstellar medium because of the abundance of atomic oxygen. The oxidation of acrylonitrile is also important in combustion as the thermal decomposition of pyrrolic and pyridinic structures present in fuel-bound nitrogen generates many nitrogen-bearing compounds, including acrylonitrile. Despite its relevance, limited information exists on this reaction. We report a combined experimental and theoretical investigation of the reactions of acrylonitrile with both ground 3P and excited 1D atomic oxygen. From product angular and time-of-flight distributions in crossed molecular beam experiments with mass spectrometric detection at a collision energy, Ec, of 31.4 kJ mol-1, we have identified the primary reaction products and determined their branching fractions (BFs). Theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) were performed to interpret the experimental results and elucidate the reaction mechanism. Adiabatic statistical calculations of product BFs for the decomposition of the main triplet and singlet intermediates have been carried out. Combining the experimental and theoretical results, we conclude that the O(3P) reaction leads to two main product channels: (i) CH2CNH (ketenimine) + CO (dominant with a BF of 0.87 ± 0.05), formed via efficient intersystem crossing from the entrance triplet PES to the underlying singlet PES, and (ii) HCOCHCN + H (minor, with a BF of 0.13 ± 0.05), occurring adiabatically on the triplet PES. Our study suggests the inclusion of this reaction as a possible destruction pathway of CH2CHCN and a possible formation route of CH2CNH in the interstellar medium. The O(1D) + CH2CHCN reaction mainly leads to the formation of CH2CNH + CO adiabatically on the singlet PES. This result can improve models related to the chemistry of interstellar ice and cometary comas, where O(1D) reactions can play a role. Overall, our results are expected to be useful for improving the models of combustion and extraterrestrial environments.

Photodissociation of permanganate (MnO4-) produces the manganese dioxide anion (MnO2-) in an excited triplet state.

Photoelectron imaging, electron action spectroscopy and electronic structure calculations are used to probe the structure and dynamics of MnO4-. Following excitation to the first bright absorption band of MnO4- (11T2), photodetachment, via ground state electron loss, and photodissociation, to produce MnO2-, are both observed to occur simultaneously. MnO2- is produced in an excited electronic state, identified as a triplet state, which indicates that the dissociation proceeds on singlet potential energy surfaces via spin conservation. Furthermore, electronic structure calculations indicate that both photodetachment and photodissociation are multiple photon processes that are mediated by the same 11T2 excited state. Taken together this data indicates that photodissociation of MnO4- occurs via a statistical dissociation on the MnO4- ground state at visible wavelengths.

The Reaction of HO2 and CH3O2: CH3OOH Formed from the Singlet Electronic State Surface

High-level coupled-cluster calculations in combination with two-dimensional master equation simulations were used to study the HO2 + CH3O2 reaction, which plays an important role in the oxidation of methane and hydrocarbons in the Earth’s atmosphere and low-temperature combustion. The main reaction pathways taking place on the lowest-lying triplet and singlet potential energy surfaces (PES) were characterized. Interestingly, methyl hydroperoxide (CH3OOH), the sole product, could be produced from both the triplet and singlet PESs, with a ratio of roughly 9:1. Formaldehyde is not made as a primary product, but can be formed via secondary chemistry. The formation of methyl tetraoxide (MTO) from the singlet PES is unimportant. The calculated reaction rate coefficients were found to be practically pressure-independent for p ≤ 760 Torr and can be given by k(T)=2.75×10−13×e+1.75 kcal mol−1/RT (in cm3/s), an expression useful for kinetics modeling over the range T = 200–800 K. The rate constant has a slight negative Arrhenius energy dependence of about −1.75 kcal mol–1, falling about a factor of 30 from 200 K to 800 K.

A DFT study on the reaction mechanisms of the oxidation of ethylene mediated by technetium and manganese oxo complexes.

The oxidation of ethylene catalyzed by manganese and technetium oxo complexes of the type MO3L (M = Tc, Mn, and L = O-, Cl-, F-, OH-, Br-, I-) on both singlet and triplet potential energy surfaces (PESs) have been studied. All molecular structures were stable on the singlet PES except for the formation of the dioxylate intermediate for the MnO3L (L = O-, Cl-, F-, OH-, Br-, I-) catalyzed pathway. Frontier molecular orbital calculations showed that electrons flow from the HOMO of ethylene into the LUMO of the metal-oxo complex for all complexes studied except for MO3L (M = Tc, Mn, and L = O-) where the vice versa occurs. In the reaction of both TcO3L and MnO3L (L = O-, Cl-, F-, OH-, Br-, I-) with ethylene, it was observed that the formation of the dioxylate intermediate along the [3 + 2] addition pathway on the singlet reaction surface is both kinetically and thermodynamically favorable over its formation via the [2 + 2] pathway. Furthermore, it was observed that TcO4- and MnO4- catalyzed pathways exclusively form diols on the singlet PES. The formation of epoxides on the singlet surface is kinetically favorable through the [2 + 1] and [2 + 2] channel for the MnO3L (L = F-, Cl-, Br-, I-, OH-) and TcO3L (L = F-, Cl-, Br-, I-, OH-) catalyzed surfaces respectively. In all cases, the TcO3L complexes were found to be polar compared to the MnO3L complexes. The MnO4- (singlet) and MnO3F (singlet) are the best catalysts for the exclusive formation of the diols and epoxides respectively.

Quantum chemical study of the reaction paths and kinetics of acetaldehyde formation on a methanol-water ice model.

Acetaldehyde (CH3CHO) is ubiquitous in interstellar space and is important for astrochemistry as it can contribute to the formation of amino acids through reaction with nitrogen containing chemical species. Quantum chemical and reaction kinetics studies are reported for acetaldehyde formation from the chemical reaction of C(3P) with a methanol molecule adsorbed at the eighth position of a cubic water cluster. We present extensive quantum chemical calculations for total spin S = 1 and S = 0. The UωB97XD/6-311++G(2d,p) model chemistry is employed to optimize the structures, compute minimum energy paths and zero-point vibrational energies of all reaction steps. For the optimized structures, the calculated energies are refined by CCSD(T) single point computations. We identify four transition states on the triplet potential energy surface (PES), and one on the singlet PES. The reaction mechanism involves the intermediate formation of CH3OCH adsorbed on the ice cluster. The rate limiting step for forming acetaldehyde is the C–O bond breaking in CH3OCH to form adsorbed CH3 and HCO. We find two positions on the reaction path where spin crossing may be possible such that acetaldehyde can form in its singlet spin state. Using variational transition-state theory with multidimensional tunnelling we provide thermal rate constants for the energetically rate limiting step for both spin states and discuss two routes to acetaldehyde formation. As expected, quantum effects are important at low temperatures.

A New Pathway for Intersystem Crossing: Unexpected Products in the O(3P) + Cyclopentene Reaction.

We investigated the reaction of O(3P) with cyclopentene at 4 Torr and 298 K using time-resolved multiplexed photoionization mass spectrometry, where O(3P) radicals were generated by 351 nm photolysis of NO2 and reacted with excess cyclopentene in He under pseudo-first-order conditions. The resulting products were sampled, ionized, and detected by tunable synchrotron vacuum ultraviolet radiation and an orthogonal acceleration time-of-flight mass spectrometer. This technique enabled measurement of both mass spectra and photoionization spectra as functions of time following the initiation of the reaction. We observe propylketene (41%), acrolein + ethene (37%), 1-butene + CO (19%), and cyclopentene oxide (3%), of which the propylketene pathway was previously unidentified experimentally and theoretically. The automatically explored reactive potential energy landscape at the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level and the related master equation calculations predict that cyclopentene oxide is formed on the singlet potential energy surface, whereas propylketene is first formed on the triplet surface. These calculations provide evidence that significant intersystem crossing can happen in this reaction not only around the geometry of the initial triplet adduct but also around that of triplet propylketene. The formation of 1-butene + CO is initiated on the triplet surface, with bond cleavage and hydrogen transfer occurring during intersystem crossing to the singlet surface. At present, we are unable to explain the mechanistic origins of the acrolein + ethene channel, and we thus refrain from assigning singlet or triplet reactivity to this channel. Overall, at least 60% of the products result from triplet reactivity. We propose that the reactivity of cyclic alkenes with O(3P) is influenced by their greater effective degree of unsaturation compared with acyclic alkenes. This work also suggests that searches for minimum-energy crossing points that connect triplet surfaces to singlet surfaces should extend beyond the initial adducts.

Theoretical study on the corrosion of thorium nuclear fuel by water: The effect of two-state reaction mechanism

The title reaction was investigated by DFT calculations. This process realizes in two steps. In the first step, singlet and triplet potential energy surfaces cross each other. We found that two-state reaction (TSR) mechanism is involved, enabling singlet product to be favored energetically. Then, ThO continues to react with H2O to form ThO2. Only the activation energy of singlet addition–elimination channel matches well with experimental reports. This work illustrates the occurrence of TSR mechanism in the corrosion of actinide nuclear fuel and further suggests a potential yet crucial impact on related fields. It deserves particular attention.

Two-state reaction guaranteed high efficiency hydrogen production in Sn+H2O reaction: A preliminarily theoretical study based on single molecule model

The Sn + H2O reaction is important in both hydrogen production through solar thermochemical redox cycles and investigations like the treatment of nuclear reactors or flame inhibition. Based on single molecule model, this work systematically explores its possible reacting channels in different spin multiplicities at CCSD(T)//DFT level of theory to reveal the underlined mechanism for its reported efficient hydrogen production. It is found that the singlet and triplet potential energy surfaces cross each other during the water attacking process, which makes the hydrogen production channel in the singlet state energetically favored. Quantitative calculations about the possibility of surface crossing and spin inversion with respect to minimum energy crossing point, spin-orbit coupling coefficient and intersystem crossing probability confirm that the optimal reacting pathway involves the two-state reaction scenario. This special reactive pattern makes hydrogen production not only possible but also efficient. Analysis of the equilibrium constant of reactive channels and their variation with temperature reveals the performance of two-state reaction channel agrees well with reported data range and nontrivial temperature dependence.