Showing papers on "Potential energy surface published in 2022"

q-AQUA: A Many-Body CCSD(T) Water Potential, Including Four-Body Interactions, Demonstrates the Quantum Nature of Water from Clusters to the Liquid Phase.

Abstract: Many model potential energy surfaces (PESs) have been reported for water; however, none are strictly from "first-principles". Here we report such a potential, based on a many-body representation at the CCSD(T) level of theory up to the four-body interaction. The new PES is benchmarked for the isomers of the water hexamer for dissociation energies, harmonic frequencies, and unrestricted diffusion Monte Carlo (DMC) calculations of the zero-point energies of the Prism, Book, and Cage isomers. Dissociation energies of several isomers of the 20-mer agree well with recent benchmark energies. Exploratory DMC calculations on this cluster verify the robustness of the new PES for quantum simulations. The accuracy and speed of the new PES are demonstrated for standard condensed phase properties, i.e., the radial distribution function and the self-diffusion constant. Quantum effects are shown to be substantial for these observables and also needed to bring theory into excellent agreement with experiment.

Fast Near Ab Initio Potential Energy Surfaces Using Machine Learning.

Abstract: A machine-learning based approach for evaluating potential energies for quantum mechanical studies of properties of the ground and excited vibrational states of small molecules is developed. This approach uses the molecular-orbital-based machine learning (MOB-ML) method to generate electronic energies with the accuracy of CCSD(T) calculations at the same cost as a Hartree-Fock calculation. To further reduce the computational cost of the potential energy evaluations without sacrificing the CCSD(T) level accuracy, GPU-accelerated Neural Network Potential Energy Surfaces (NN-PES) are trained to geometries and energies that are collected from small-scale Diffusion Monte Carlo (DMC) simulations, which are run using energies evaluated using the MOB-ML model. The combined NN+(MOB-ML) approach is used in variational calculations of the ground and low-lying vibrational excited states of water and in DMC calculations of the ground states of water, CH5+, and its deuterated analogues. For both of these molecules, comparisons are made to the results obtained using potentials that were fit to much larger sets of electronic energies than were required to train the MOB-ML models. The NN+(MOB-ML) approach is also used to obtain a potential surface for C2H5+, which is a carbocation with a nonclassical equilibrium structure for which there is currently no available potential surface. This potential is used to explore the CH stretching vibrations, focusing on those of the bridging hydrogen atom. For both CH5+ and C2H5+ the MOB-ML model is trained using geometries that were sampled from an AIMD trajectory, which was run at 350 K. By comparison, the structures sampled in the ground state calculations can have energies that are as much as ten times larger than those used to train the MOB-ML model. For water a higher temperature AIMD trajectory is needed to obtain accurate results due to the smaller thermal energy. A second MOB-ML model for C2H5+ was developed with additional higher energy structures in the training set. The two models are found to provide nearly identical descriptions of the ground state of C2H5+.

Permutation-Invariant-Polynomial Neural-Network-Based Δ-Machine Learning Approach: A Case for the HO2 Self-Reaction and Its Dynamics Study.

Abstract: Δ-machine learning, or the hierarchical construction scheme, is a highly cost-effective method, as only a small number of high-level ab initio energies are required to improve a potential energy surface (PES) fit to a large number of low-level points. However, there is no efficient and systematic way to select as few points as possible from the low-level data set. We here propose a permutation-invariant-polynomial neural-network (PIP-NN)-based Δ-machine learning approach to construct full-dimensional accurate PESs of complicated reactions efficiently. Particularly, the high flexibility of the NN is exploited to efficiently sample points from the low-level data set. This approach is applied to the challenging case of a HO2 self-reaction with a large configuration space. Only 14% of the DFT data set is used to successfully bring a newly fitted DFT PES to the UCCSD(T)-F12a/AVTZ quality. Then, the quasiclassical trajectory (QCT) calculations are performed to study its dynamics, particularly the mode specificity.

Cavity-altered thermal isomerization rates and dynamical resonant localization in vibro-polaritonic chemistry

Abstract: It has been experimentally demonstrated that reaction rates for molecules embedded in microfluidic optical cavities are altered when compared to rates observed under "ordinary" reaction conditions. However, precise mechanisms of how strong coupling of an optical cavity mode to molecular vibrations affects the reactivity and how resonance behavior emerges are still under dispute. In the present work, we approach these mechanistic issues from the perspective of a thermal model reaction, the inversion of ammonia along the umbrella mode, in the presence of a single-cavity mode of varying frequency and coupling strength. A topological analysis of the related cavity Born-Oppenheimer potential energy surface in combination with quantum mechanical and transition state theory rate calculations reveals two quantum effects, leading to decelerated reaction rates in qualitative agreement with experiments: the stiffening of quantized modes perpendicular to the reaction path at the transition state, which reduces the number of thermally accessible reaction channels, and the broadening of the barrier region, which attenuates tunneling. We find these two effects to be very robust in a fluctuating environment, causing statistical variations of potential parameters, such as the barrier height. Furthermore, by solving the time-dependent Schrödinger equation in the vibrational strong coupling regime, we identify a resonance behavior, in qualitative agreement with experimental and earlier theoretical work. The latter manifests as reduced reaction probability when the cavity frequency ωc is tuned resonant to a molecular reactant frequency. We find this effect to be based on the dynamical localization of the vibro-polaritonic wavepacket in the reactant well.

Unsaturated Dinitriles Formation Routes in Extraterrestrial Environments: A Combined Experimental and Theoretical Investigation of the Reaction between Cyano Radicals and Cyanoethene (C2H3CN)

Abstract: The reaction between cyano radicals (CN, X2Σ+) and cyanoethene (C2H3CN) has been investigated by a combined approach coupling crossed molecular beam (CMB) experiments with mass spectrometric detection and time-of-flight analysis at a collision energy of 44.6 kJ mol–1 and electronic structure calculations to determine the relevant potential energy surface. The experimental results can be interpreted by assuming the occurrence of a dominant reaction pathway leading to the two but-2-enedinitrile (1,2-dicyanothene) isomers (E- and Z-NC–CH=CH–CN) in a H-displacement channel and, to a much minor extent, to 1,1-dicyanoethene, CH2C(CN)2. In order to derive the product branching ratios under the conditions of the CMB experiments and at colder temperatures, including those relevant to Titan and to cold interstellar clouds, we have carried out RRKM statistical calculations using the relevant potential energy surface of the investigated reaction. We have also estimated the rate coefficient at very low temperatures by employing a semiempirical method for the treatment of long-range interactions. The reaction has been found to be barrierless and fast also under the low temperature conditions of cold interstellar clouds and the atmosphere of Titan. Astrophysical implications and comparison with literature data are also presented. On the basis of the present work, 1,2-dicyanothene and 1,1-dicyanothene are excellent candidates for the search of dinitriles in the interstellar medium.

Quantum Calculations on a New CCSD(T) Machine-Learned Potential Energy Surface Reveal the Leaky Nature of Gas-Phase Trans and Gauche Ethanol Conformers

Abstract: Ethanol is a molecule of fundamental interest in combustion, astrochemistry, and condensed phase as a solvent. It is characterized by two methyl rotors and trans (anti) and gauche conformers, which are known to be very close in energy. Here we show that based on rigorous quantum calculations of the vibrational zero-point state, using a new ab initio potential energy surface (PES), the ground state resembles the trans conformer, but substantial delocalization to the gauche conformer is present. This explains experimental issues about identification and isolation of the two conformers. This “leak” effect is partially quenched when deuterating the OH group, which further demonstrates the need for a quantum mechanical approach. Diffusion Monte Carlo and full-dimensional semiclassical dynamics calculations are employed. The new PES is obtained by means of a Δ-machine learning approach starting from a pre-existing low level density functional theory surface. This surface is brought to the CCSD(T) level of theory using a relatively small number of ab initio CCSD(T) energies. Agreement between the corrected PES and direct ab initio results for standard tests is excellent. One- and two-dimensional discrete variable representation calculations focusing on the trans–gauche torsional motion are also reported, in reasonable agreement with experiment.

Benchmarking PES‐Learn's machine learning models predicting accurate potential energy surface for quantum scattering

Abstract: Machine learning (ML) models, neural networks, and Gaussian processes have been used to predict the potential energy surface taking C2-He (both static and dynamic scenario) and NCCN-He collision systems. The surface is restricted to ∽125 points where traditional spline becomes inefficacious. Quantum dynamics is performed by solving close-coupling equation to compute cross sections benchmarking the performance of the ML models. The current study forms a basis for any future investigation of larger molecules where conventional fitting fails due to sparser ab initio points and cuts down the computational time without compromising on the quality of the surface.

Validating experiments for the reaction H2 + NH2- by dynamical calculations on an accurate full-dimensional potential energy surface.

Abstract: Ion-molecule reactions play key roles in the field of ion related chemistry. As a prototypical multi-channel ion-molecule reaction, the reaction H2 + NH2- → NH3 + H- has been studied for decades. In this work, we develop a new globally accurate potential energy surface (PES) for the title system based on hundreds of thousands of sampled points over a wide dynamically relevant region that covers long-range interacting configuration space. The permutational invariant polynomial-neural network (PIP-NN) method is used for fitting and the resulting total root mean squared error (RMSE) is extremely small, 0.026 kcal mol-1. Extensive dynamical and kinetic calculations are carried out on this PIP-NN PES. Impressively, a unique phenomenon of significant reactivity suppression by exciting the rotational mode of H2 is reported, supported by both the quasi-classical trajectory (QCT) and quantum dynamics (QD) calculations. Further analysis uncovers that exciting the H2 rotational mode would prevent the formation of the reactant complex and thus suppress the reactivity. The calculated rate coefficients for H2/D2 + NH2- agree well with the experimental results, which show an inverse temperature dependence from 50 to 300 K, consistent with the capture nature of this barrierless reaction. The significant kinetic isotope effect observed by experiments is well reproduced by the QCT computations as well.

ManyHF: A pragmatic automated method of finding lower-energy Hartree-Fock solutions for potential energy surface development.

Abstract: Developing global, high-dimensional potential energy surfaces (PESs) is a formidable task. Beside the challenges of PES fitting and fitting set generation, one also has to choose an electronic structure method capable of delivering accurate potential energy values for all geometries in the fitting set, even in regions far from equilibrium. Such regions are often plagued by Hartree-Fock (HF) convergence issues, and even if convergence is achieved, self-consistent field (SCF) procedures that are used to obtain HF solutions offer no guarantee that the solution found is the lowest-energy solution. We present a study of the reactant regions of CH3OH + OH·, C2H6 + F·, and CH3NH2 + Cl·, where the SCF procedure often converges to a higher-energy state or fails to converge, resulting in erratic post-HF energies and regions where no energy is obtained, both of which are major obstacles for PES development. We introduce a pragmatic method for automatically finding better HF solutions (dubbed ManyHF) and present evidence that it may extend the applicability of single-reference methods to some systems previously thought to require multireference methods.

Fewest switches surface hopping with Baeck-An couplings

Abstract: In the Baeck-An (BA) approximation, first-order nonadiabatic coupling vectors are given in terms of adiabatic energy gaps and the second derivative of the gaps with respect to the coupling coordinate. In this paper, a time-dependent (TD) BA approximation is derived, where the couplings are computed from the energy gaps and their second time-derivatives. TD-BA couplings can be directly used in fewest switches surface hopping, enabling nonadiabatic dynamics with any electronic structure methods able to provide excitation energies and energy gradients. Test results of surface hopping with TD-BA couplings for ethylene and fulvene show that the TD-BA approximation delivers a qualitatively correct picture of the dynamics and a semiquantitative agreement with reference data computed with exact couplings. Nevertheless, TD-BA does not perform well in situations conjugating strong couplings and small velocities. Considered the uncertainties in the method, TD-BA couplings could be a competitive approach for inexpensive, exploratory dynamics with a small trajectories ensemble. We also assessed the potential use of TD-BA couplings for surface hopping dynamics with time-dependent density functional theory (TDDFT), but the results are not encouraging due to singlet instabilities near the crossing seam with the ground state.

The Role of Methylaryl Radicals in the Growth of Polycyclic Aromatic Hydrocarbons: The Formation of Five-Membered Rings.

Abstract: The regions of the C13H11 potential energy surface (PES) related to the unimolecular isomerization and decomposition of the 1-methylbiphenylyl radical and accessed by the 1-/2-methylnaphthyl + C2H2 reactions have been explored by ab initio G3(MP2,CC)//B3LYP/6-311G(d,p) calculations. The kinetics of these reactions relevant to the growth of polycyclic aromatic hydrocarbons (PAH) under high-temperature conditions in circumstellar envelopes and in combustion flames has been studied employing the RRKM-Master Equation approach. The unimolecular reaction of 1-methylbiphenylyl proceeding via a five-membered ring closure followed by H elimination is predicted to be very fast, on a submicrosecond scale above 1000 K and to result in the formation of an embedded five-membered ring in the 9H-fluorene product. The 1-/2-methylnaphthyl + C2H2 reaction mechanism involves acetylene addition to the radical on the methylene group followed by a six- or five-membered ring closure and aromatization via an H atom loss. Despite of the complexity of the C13H11 PES, these straightforward pathways are dominant in the high-temperature regime (above ∼1000 K), with the prevailing products being phenalene, with a significant contribution of 1H-cyclopenta(a)naphthalene, for 1-methylnaphthyl + C2H2, and 1H-cyclopenta(b)naphthalene and 3H-cyclopenta(a)naphthalene, for 2-methylnaphthyl + C2H2. The methylnaphthyl reactions with acetylene represent a clean source of the three-ring PAHs, but they are relatively slow owing to the high entrance barriers of ∼10 kcal/mol, with the rate constants of about an order of magnitude lower as compared to those for naphthyl + allene and σ-aryl + C2H2. The 1-methylnaphthyl + C2H2 and 2-methylnaphthyl + C2H2 reactions represent prototypes for PAH growth by an extra six- and five-membered ring on a zigzag edge or a corner of PAH and the generated modified Arrhenius expressions are recommended for kinetic modeling of PAH expansion by the mechanism of acetylene addition to methylaryl radicals.

Three-body potential energy surface for para-hydrogen.

Abstract: We present a 3D isotropic ab initio three-body (para-H2)3 interaction potential energy surface (PES). The electronic structure calculations are carried out at the correlated coupled-cluster theory level, with single, double, and perturbative triple excitations. The calculations use an augmented correlation-consistent triple zeta basis set and a supplementary midbond function. We construct the PES using the reproducing-kernel Hilbert space toolkit [O. T. Unke and M. Meuwly, J. Chem. Inf. Model. 57, 1923 (2017)] with phenomenological and empirical adjustments to account for short-range and long-range behaviors. The (para-H2)3 interaction energies deviate drastically from the Axilrod-Teller-Muto (ATM) potential at short intermolecular separations. We find that the configuration of three para-H2 molecules at the corners of an equilateral triangle is responsible for the majority of the (para-H2)3 interaction energy contribution in a hexagonal-close-packed lattice. In cases where two para-H2 molecules are close to one another while the third is far away, the (para-H2)3 interaction PES takes the form of a modified version of the ATM potential. We expect the combination of this PES together with a first-principles para-H2-para-H2 adiabatic hindered rotor potential to outperform a widely used effective pair potential for condensed many-body systems of para-H2.

First-Principles Insights into Adiabatic and Nonadiabatic Vibrational Energy-Transfer Dynamics during Molecular Scattering from Metal Surfaces: The Importance of Surface Reactivity.

Abstract: Energy transfer is ubiquitous during molecular collisions and reactions at gas-surface interfaces. Of particular importance is vibrational energy transfer because of its relevance to bond forming and breaking. In this Perspective, we review recent first-principles studies on vibrational energy-transfer dynamics during molecular scattering from metal surfaces at the state-to-state level. Taking several representative systems as examples, we highlight the intrinsic correlation between vibrational energy transfer in nonreactive scattering and surface reactivity and how it operates in both electronically adiabatic and nonadiabatic pathways. Adiabatically, the presence of a dissociation barrier softens a bond in the impinging molecule and increases its couplings with other molecular modes and surface phonons. In the meantime, the stronger interaction between the molecule and the surface also changes the electronic structure at the barrier, resulting in an increase of nonadiabatic effects. We further discuss future prospects toward a more quantitative understanding of this important surface dynamical process.

Taming Disulfide Bonds with Laser Fields. Nonadiabatic Surface-Hopping Simulations in a Ruthenium Complex

Abstract: Laser control of chemical reactions is a challenging field of research. In particular, the theoretical description of coupled electronic and nuclear motion in the presence of laser fields is not a trivial task and simulations are mostly restricted to small systems or molecules treated within reduced dimensionality. Here, we demonstrate how the excited state dynamics of [Ru(S–Sbpy)(bpy)2]2+ can be controlled using explicit laser fields in the context of fewest-switches surface hopping. In particular, the transient properties along the excited state dynamics leading to population of the T1 minimum energy structure are exploited to define simple laser fields capable of slowing and even completely stopping the onset of S–S bond dissociation. The use of a linear vibronic coupling model to parametrize the potential energy surfaces showcases the strength of the surface-hopping methodology to study systems including explicit laser fields using many nuclear degrees of freedom and a large amount of close-lying electronic excited states.

Unconventional SN2 retention pathways induced by complex formation: High-level dynamics investigation of the NH2 - + CH3I polyatomic reaction.

Abstract: Investigations on the dynamics of chemical reactions have been a hot topic for experimental and theoretical studies over the last few decades. Here, we carry out the first high-level dynamical characterization for the polyatom-polyatom reaction between NH2 - and CH3I. A global analytical potential energy surface is developed to describe the possible pathways with the quasi-classical trajectory method at several collision energies. In addition to SN2 and proton abstraction, a significant iodine abstraction is identified, leading to the CH3 + [NH2⋯I]- products. For SN2, our computations reveal an indirect character as well, promoting the formation of [CH3⋯NH2] complexes. Two novel dominant SN2 retention pathways are uncovered induced by the rotation of the CH3 fragment in these latter [CH3⋯NH2] complexes. Moreover, these uncommon routes turn out to be the most dominant retention paths for the NH2 - + CH3I SN2 reaction.

General Analytical Nuclear Forces and Molecular Potential Energy Surface from Full Configuration Interaction Quantum Monte Carlo.

Abstract: The full configuration interaction quantum Monte Carlo (FCIQMC) is a state-of-the-art stochastic electronic structure method, providing a methodology to compute FCI-level state energies of molecular systems within a quantum chemical basis. However, especially to probe dynamics at the FCIQMC level, it is necessary to devise more efficient schemes to produce nuclear forces and potential energy surfaces (PES) from FCIQMC. In this work, we derive the general formula for nuclear forces from FCIQMC, and clarify different contributions of the total force. This method to obtain FCIQMC forces eliminates previous restrictions and can be used with frozen core approximation and free selection of orbitals, making it promising for more efficient nuclear forces calculations. After some numerical checks of this procedure on the binding curve of N2 molecule, we use the FCIQMC energy and force to obtain the full-dimensional ground state PES of the water molecule via Gaussian processes regression. The new water FCIQMC PES can be used as the basis for H2O ground state nuclear dynamics, structure optimization, and rotation-vibrational spectrum calculation.

Quantitative dynamics of paradigmatic SN2 reaction OH- + CH3F on accurate full-dimensional potential energy surface.

Abstract: The bimolecular reaction between OH- and CH3F is not just a prototypical SN2 process, but it has three other product channels. Here, we develop an accurate full-dimensional potential energy surface (PES) based on 191 193 points calculated at the level CCSD(T)-F12a/aug-cc-pVTZ. A detailed dynamics and mechanism analysis was carried out on this potential energy surface using the quasi-classical trajectory approach. It is verified that the trajectories do not follow the minimum energy path (MEP), but directly dissociate to F- and CH3OH. In addition, a new transition state for proton exchange and a new product complex CH2F-⋯H2O for proton abstraction were discovered. The trajectories avoid the transition state or this complex, instead dissociate to H2O and CH2F- directly through the ridge regions of the minimum energy path before the transition state. These non-MEP dynamics become more pronounced at high collision energies. Detailed dynamic simulations provide new insights into the atomic-level mechanisms of the title reaction, thanks to the new chemically accurate PES, with the aid of machine learning.

Substituents affect the mechanism of photochemical E-Z isomerization of diarylethene triazoles via adiabatic singlet excited state pathway or via triplet excited state

Abstract: Photochemical reactivity in the Z-E isomerization for two heterostilbene derivatives containing 1,2,3-triazole unit were investigated theoretically and experimentally by irradiation experiments, fluorescence and laser flash photolysis (LFP). The molecules were designed to probe the effect of the para-nitro group in 1 on the photochemical E-Z pathways, as well as to investigate the steric effect of the ortho-methyl group in 2. The quantum yield for the Z → E isomerization for both cis-isomers is 0.42, and for the E → Z is somewhat lower 0.16 and 0.12, respectively. Furthermore, fluorescence measurements for the ortho-methyl derivative indicated that the Z → E isomerization takes place in an adiabatic reaction on the potential energy surface of the S1 state. On the contrary, the para-nitro derivative undergoes the Z → E isomerization via a triplet excited state, which was detected by LFP. For both cis- and trans-isomers of the nitro derivative a transient was detected absorbing with a maximum at 520 nm, which was assigned to the triplet excited state of the trans-isomer. All experimental observations were corroborated by computations. The stationary points were computed at the PBE50/6-31++G** level of theory, whereas potential energy surfaces were obtained by linear interpolation and computations at the SF-TDDFT/PBE50/6-31++G** level of theory. The mechanistic investigation presented gives insight in the fundamental and simple Z → E isomerization and provides new findings which are important in the rational design of different photoreactive diarylethene derivatives used in different fields of science.

Ring-Polymer Molecular Dynamics and Kinetics for the H- + C2H2 → H2 + C2H- Reaction Using the Full-Dimensional Potential Energy Surface.

Abstract: The H- + C2H2 → H2 + C2H- reaction is important in understanding the production mechanisms of anionic molecules in interstellar environments. Herein, the rate coefficients for the H- + C2H2 → H2 + C2H- reaction were calculated using ring-polymer molecular dynamics (RPMD), classical molecular dynamics (MD), and quasi-classical trajectory (QCT) approaches on a newly developed ab initio potential energy surface (PES) in full dimensions. PES was constructed by fitting a large number of ab initio energy points and their gradients using the permutationally invariant polynomial basis set method. There was no barrier in the reaction coordinates, which was a collinear-dominated reaction, and the reaction proceeded exothermically. It is found that the fitted PES provides the appropriate thermal rate coefficients based on all RPMD, classical MD, and QCT simulations at higher temperatures. The evaluation of the rate coefficients at lower temperatures should be conducted carefully because the fitting of the PES associated with the long-range interaction should be further improved. The spatial distribution of the nucleus allows a more effective attraction between the reactants.

Rotational excitation of NS+ by H2 revisited: A new global potential energy surface and rate coefficients.

Abstract: Due to the lack of specific collisional data, the abundance of NS+ in cold dense interstellar clouds was determined using collisional rate coefficients of CS as a substitute. To better understand the chemistry of sulfur in the interstellar medium, further abundance modeling using the actual NS+ collisional rate coefficients is needed. For this purpose, we have computed the first full 4D potential energy surface of the NS+-H2 van der Waals complex using the explicitly correlated coupled cluster approach with single, double, and non-iterative triple excitation in conjunction with the augmented-correlation consistent-polarized valence triple zeta basis set. The potential energy surface exhibits a global minimum of 848.24 cm-1 for a planar configuration of the complex. The long-range interaction energy, described using multipolar moments, is sensitive to the orientation of H2 up to radial distances of ∼50 a0. From this new interaction potential, we derived excitation cross sections, induced by collision with ortho- and para-H2, for the 15 low-lying rotational levels of NS+ using the quantum mechanical close-coupling approach. By thermally averaging these data, we determined downward rate coefficients for temperatures up to 50 K. By comparing them with the previous NS+-H2 data, we demonstrated that reduced dimensional approaches are not suited for this system. In addition, we found that the CS collisional data underestimate our results by up to an order of magnitude. The differences clearly indicate that the abundance of NS+, in cold dense clouds retrieved from observational spectra, must be reassessed using these new collisional rate coefficients.

Gliding on Ice in Search of Accurate and Cost-Effective Computational Methods for Astrochemistry on Grains: The Puzzling Case of the HCN Isomerization

Abstract: The isomerization of hydrogen cyanide to hydrogen isocyanide on icy grain surfaces is investigated by an accurate composite method (jun-Cheap) rooted in the coupled cluster ansatz and by density functional approaches. After benchmarking density functional predictions of both geometries and reaction energies against jun-Cheap results for the relatively small model system HCN···(H2O)2, the best performing DFT methods are selected. A large cluster containing 20 water molecules is then employed within a QM/QM′ approach to include a realistic environment mimicking the surface of icy grains. Our results indicate that four water molecules are directly involved in a proton relay mechanism, which strongly reduces the activation energy with respect to the direct hydrogen transfer occurring in the isolated molecule. Further extension of the size of the cluster up to 192 water molecules in the framework of a three-layer QM/QM′/MM model has a negligible effect on the energy barrier ruling the isomerization. Computation of reaction rates by the transition state theory indicates that on icy surfaces, the isomerization of HNC to HCN could occur quite easily even at low temperatures thanks to the reduced activation energy that can be effectively overcome by tunneling.

Theoretical dynamics studies of the CH3 + HBr → CH4 + Br reaction: integral cross sections, rate constants and microscopic mechanism.

Abstract: Quantum and quasi-classical dynamics calculations have been performed for the reaction of HBr with CH3. The accurate ab initio-based potential energy surface function developed earlier for this reaction displays a potential well corresponding to a reactant complex and a submerged potential barrier. The integral cross sections were calculated on this potential energy surface using both a six-degree-of-freedom reduced dimensional quantum dynamics and the quasi-classical trajectory method and very good agreement was found between the two approaches. The cross sections were found to diverge when the collision energy decreases, indicating that the reactant attraction is responsible for the dynamics at low collision energy. The quantum mechanical and the quasi-classical rate constants also agree very well and almost exactly reproduce the experimental results at low temperatures up to 540 K. The negative activation energy observed experimentally is confirmed by the calculations and is a consequence of the long-range attraction between the reactants. From the classical trajectories mechanistic details have been extracted. It is found that at very low collision energy, the reacting system crosses the potential barrier because the forces within the complex guide them, although some 30% is reflected from the product side of the barrier. When the collision energy increases, the system does not follow the most favorable path and the reactants are, with increasing probability, reflected from the repulsive walls of the nonreactive parts of the reactants, providing a picture beyond the decreasing excitation function.