Analytical Potential Energy Surface Research Articles

Dynamics of the HCl + C2H5 Multichannel Reaction on a Full-Dimensional Ab Initio Potential Energy Surface.

We report a full-dimensional ab initio analytical potential energy surface (PES), which accurately describes the HCl + C2H5 multichannel reaction. The new PES is developed by iteratively adding selected configurations along HCl + C2H5 quasi-classical trajectories (QCTs), thereby improving our previous Cl(2P3/2) + C2H6 PES using the Robosurfer program package. QCT simulations for the H'Cl + C2H5 reaction reveal hydrogen-abstraction, chlorine-abstraction, and hydrogen-exchange channels leading to Cl + C2H5H', H' + C2H5Cl, and HCl + C2H4H', respectively. Hydrogen abstraction dominates in the collision energy (Ecoll) range of 1-80 kcal/mol and proceeds with indirect isotropic scattering at low Ecoll and forward-scattered direct stripping at high Ecoll. Chlorine abstraction opens around 40 kcal/mol collision energy and becomes competitive with hydrogen abstraction at Ecoll = 80 kcal/mol. A restricted opening of the cone of acceptance in the Cl-abstraction reaction is found to result in the preference for a backward-scattering direct-rebound mechanism at all energies studied. Initial attack-angle distributions show mainly side-on collision preference of C2H5 for both abstraction reactions, and in the case of the HCl reactant, H/Cl-side preference for the H/Cl abstraction. For hydrogen abstraction, the collision energy transfer into the product translational and internal energy is almost equally significant, whereas in the case of chlorine abstraction, most of the available energy goes into the internal degrees of freedom. Hydrogen exchange is a minor channel with nearly constant reactivity in the Ecoll range of 10-80 kcal/mol.

Intramolecular Catalytic Hydrogen Atom Transfer (CHAT).

Intramolecular catalysis (IntraCat) is the acceleration of a process at one site of a molecule catalyzed by a functional group in the same molecule; an external agent such as a solvent typically facilitates it. Here, we report a general first-principles-based IntraCat mechanism, which strictly occurs within a single molecule with no coreagent being involved─we call it intramolecular catalytic transfer of hydrogen atoms (CHAT). A reactive part of a molecule (chat catalyst moiety or chat agent, represented by -OOH, -COOH, -SH, -CH2OH, -HPO4, or another bifunctional H-donor/acceptor group) catalyzes an interconversion process, such as keto-enol or amino-imino tautomerization, and cyclization in the same molecule, while being regenerated in the process. It can thus be regarded as an intramolecular version of the intermolecular H atom transfer processes mediated by an external molecular catalyst, e.g., dihydrogen, water, or a carboxylic acid. Earlier, we proposed a general mechanistic systematization of intermolecular processes, illustrated in the simplest case of the H2-mediated reactions classified as dihydrogen catalysis [Asatryan, R.; et al. Catal. Rev.: Sci. Eng., 2014, 56, 403-475]. Following this systematization, the CHAT catalysis belongs to the category of relay transfer of H atoms, albeit in an intramolecular manner. A broader class of intramolecular processes includes all types of H-transfer reactions stimulated by an H-migration, which we call self-catalyzed H atom transfer (SC-HAT). The CHAT mechanism comprises a subset of SC-HAT in which the catalytic moiety is regenerated (i.e., acts as a true catalyst and not a reagent). We provide several characteristic examples of CHAT mechanism based on detailed analysis of the corresponding potential energy surfaces. All such cases showed a dramatically reduced activation barrier relative to the corresponding uncatalyzed H-transfer reactions. For example, we show that CHAT can facilitate long-range H-migration in larger molecules and can occur multiple times in one molecule with multiple interconverting groups. It also facilitates amino-imino tautomerization of unsaturated GABA-analogues and peptides, as well as intramolecular cyclization processes to form heterocycles, e.g., oxygenated rings. CHAT pathways may also explain the pH-dependent increase of mutarotation rate of glucose-6-phosphate demonstrated in pioneering experiments that introduced the classical IntraCat concept. In addition, we identify a ground electronic state CHAT pathway as an alternative to the UV-promoted long-range molecular crane keto-enol conversion with a remarkably low activation energy. To initially assess the possible impact of the new keto-enol conversion pathway on combustion of n-alkanes, we present a detailed kinetic analysis of isomerization and decomposition of pentane-2,4-ketohydroperoxide (2,4-KHP). The results are compared with key alternative reactions, including direct dissociation and Korcek channels (for which a new alkyl group migration channel is also identified), revealing the competitiveness of the CHAT pathway across a range of conditions. Taken together, this work provides insight into a general class of reaction pathways that has not previously being systematically considered and that may occur in a broad range of contexts from combustion to atmospheric chemistry to biochemistry.

Theoretical dynamics studies of the CH3 + HBr → CH4 + Br reaction: effects of isotope substitution and vibrational excitation of CH3.

The rate coefficient for two deuterium substituted isotopologues of reaction CH3 + HBr → CH4 + Br has been determined using the quasiclassical trajectory (QCT) method. We used the analytical potential energy surface (PES) fitted to high-level ab initio points in earlier work. The PES exhibits a pre-reaction van der Waals complex and a submerged potential barrier. The rate coefficients of the deuterated isotopologue reactions, similarly to the pure-protium isotopologue, show significant deviation from the Arrhenius law, namely, the activation energy is negative below about 600 K and positive above it: k[CH3 + DBr] = 1.35 × 10-11 exp(- 2472/T) + 5.85 × 10-13 exp(335/T) and k[CD3 + HBr] = 2.73 × 10-11 exp(- 2739/T) + 1.46 × 10-12 exp(363/T). The CH3 + DBr reaction is slower by a factor of 1.8, whereas CD3 + HBr isotopologue is faster by a factor of 1.4 compared to the HBr + CH3 system across a wide temperature range. The isotope effects are interpreted in terms of the properties of various regions of the PES. Quantum state-resolved simulations revealed that the reaction of CH3 with HBr becomes slower when any of the vibrational modes of the methyl radical is excited. This contradicts the assumption that vibrational excitation of methyl radicals enhances its reactivity, which is of historical importance: this assumption was used as an argument against the existence of negative activation energy in a decade-long controversy in the 1980s and 1990s.

High-temperature spectra of the PNO molecule based on robust first-principles methods.

The PNO molecule is an important species found in the interstellar medium, and its spectroscopic information is helpful for its detection. We present the first line list of PNO (X1Σ+) using robust first-principles methods. The analytical potential energy surface and the dipole moment surface were constructed based on 11 942 ab initio points. The variational nuclear motion calculation was implemented in TROVE to obtain the rovibrational energy levels, Einstein A coefficients and other parameters. The J-dependent Coriolis-decoupled Hamiltonian was adopted with k ≤ 15, and the l-type doubling was considered for the bending vibration of the linear molecule. The line list contained almost 5.87 billion transitions between 3.61 million levels with rotational excitation up to J = 200 and was used to generate the PNO spectrum below 3000 K in the wavenumber range from 0 to 6000 cm-1. The millimetre wave spectrum agrees well with available experimental benchmarks. The Fermi resonance effects in the PNO spectrum are universal and complex, resulting in significant intensity increment of the related weak transition. This line list may be helpful for the spectroscopic characterization and possible astronomical detection of PNO, especially in high-temperature environments.

Kinetic study of the CN + C2H6 hydrogen abstraction reaction based on an analytical potential energy surface.

The temperature dependence of the thermal rate constants and kinetic isotope effects (KIE) of the CN + C2H6 gas-phase hydrogen abstraction reaction was theoretically determined within the 25-1000 K temperature range, i.e., from very low- to high-temperature regimes. Based on a recently developed full-dimensional analytical potential energy surface fitted to highly accurate explicitly correlated ab initio calculations, three different kinetic theories were used: canonical variational transition state theory (CVT), quasiclassical trajectory theory (QCT), and ring polymer molecular dynamics (RPMD) method for the computation of rate constants. We found that the thermal rate constants obtained with the three theories show a V-shaped temperature dependence, with a pronounced minimum near 200 K, qualitatively reproducing the experimental measurements. Among the three methods used in this work, the QCT and RPMD methods have the best agreement with the experiment at low and high temperatures, respectively, while the CVT model shows the largest discrepancies. The significant increase in the rate constant at very low temperatures in this very exothermic and practically barrierless reaction could be attributed to the large value of the impact parameter, possibly ruling out the role of the tunneling effect and the intermediate complexes in the entrance channel. The theoretical H/D KIE depicted a "normal" behaviour, i.e., values greater than unity, emulating the experimental measurements and improving previous theoretical results. Finally, the discrepancies between theory and experiments were analysed as a function of several factors, such as limitations of the kinetics theories and the potential energy surface, as well as the uncertainties in the experimental measurements.

Predictive study, using density functional theory and time dependent functional theory, on the structure-property quantification of methylene blue and methyl red dyes for the application in organic solar cells

In this work, two organic materials as dyes, namely, methylene blue (MB) and methyl red (MR), have been proposed to play the role of the electron donor in organic photovoltaic (OPV) cells. We use the PCBM as a well-known electron acceptor. The density functional theory (DFT) method has been used to determine the electrostatic potential and the frontier molecular orbitals (FMO), of the methylene blue (MB) and the methyl red (MR) compounds. Nonlinear optical (NLO) descriptors have been determined for the two compounds. The potential energy surface analysis has been performed by the DFT method using the exchange and correlation of Becke, Lee, Yang, and Parr Gradient Corrected Functional (B3LYP) with the standard 6-31G(d) base. We have performed another theoretical study using quantum time-dependent density functional theory (TD-DFT) on both MB and MR as organic dyes to determine their UV-Vis spectra. The results of the energy gap, chemical hardness, dipole moment, and hyperpolarizability show that MB may be chemically more reactive Than MR. The present work has proposed a bilayer organic photovoltaic (OPV) cell to contribute to the valorization of the two dyes as solar materials. The developed photovoltaic cell project has used electrical and energetic parameters that can describe the OPV cell based on ([MB or MR]: PCBM). Open-circuit voltage (Voc), excitation energy, and oscillator strength have been theoretically determined. The results of the present work showed a remarkably high open circuit voltage, especially in the case of methyl red (1.55 V) more than in the case of the methylene blue (0.84 V) so that both of the two dyes can be a good candidate for organic solar cells.

Detailed quasiclassical dynamics of the F- + SiH3Cl multi-channel reaction.

We report a detailed quasiclassical trajectory study on the F- + SiH3Cl multi-channel reaction using a full-dimensional ab initio analytical potential energy surface. Reaction probabilities, cross sections, initial attack and scattering angle distributions as well as product relative translational, internal, vibrational, and rotational energy distributions are obtained in the collision energy range of 1-40 kcal mol-1 for the following channels: SiH3F + Cl-, SiH2Cl- + HF, SiH2F- + HCl, SiH2FCl + H-, SiH2 + FHCl-, and SiHFCl- + H2. All the channels are translationally cold indicating indirect mechanisms, except proton transfer (SiH2Cl- + HF), which shows mixed direct-indirect character. The angular distributions vary depending on collision energy and inversion/retention for SiH3F + Cl-. In the case of SiH2Cl- + HF front-side/back-side attack backward-forward/forward scattering preference is found at low/high collision energy. SiH2F- + HCl is formed with isotropic scattering and the preferred angle of attack is similar to the SiH3F + Cl- channel. SiH2FCl + H-/SiH2 + FHCl- favors back-side attack and isotropic/backward scattering, whereas SiHFCl- + H2 does not show significant angular preference.

First-principles mode-specific reaction dynamics.

Controlling the outcome of chemical reactions by exciting specific vibrational and/or rotational modes of the reactants is one of the major goals of modern reaction dynamics studies. In the present Perspective, we focus on first-principles vibrational and rotational mode-specific dynamics computations on reactions of neutral and anionic systems beyond six atoms such as X + C2H6 [X = F, Cl, OH], HX + C2H5 [X = Br, I], OH- + CH3I, and F- + CH3CH2Cl. The dynamics simulations utilize high-level ab initio analytical potential energy surfaces and the quasi-classical trajectory method. Besides initial state specificity and the validity of the Polanyi rules, mode-specific vibrational-state assignment for polyatomic product species using normal-mode analysis and Gaussian binning is also discussed and compared with experiment.

ANT 2023: A program for adiabatic and nonadiabatic trajectories

ANT 2023 is a program for quasiclassical and semiclassical trajectories, both single-surface trajectories for which the Born-Oppenheimer approximation is valid and multi-surface calculations with electronic state changes, i.e., for electronically adiabatic and electronically nonadiabatic trajectories. There are several methods available for multisurface problems: surface hopping with or without time uncertainty and with or without decoherence, semiclassical Ehrenfest, self-consistent decay of mixing, and coherent switching with decay of mixing (CSDM). The potential surface for single-surface problems may be an analytic potential function supplied by the user, or one may use direct dynamics. To use the adiabatic representation (i.e., electronically adiabatic basis functions) for electronically nonadiabatic dynamics, the user may either provide the adiabatic surfaces and nonadiabatic couplings by direct dynamics, or the program may calculate them from diabatic surfaces and diabatic couplings, which are usually analytic. One can also use analytic fits to the surfaces and couplings to carry out calculations entirely in the diabatic representation. The curvature-driven approximation is available as an option for use with CSDM and trajectory surface hopping. The ANT 2023 program is especially recommended for calculations with analytic potential energy surfaces and couplings because of its high efficiency for such calculations. Program SummaryProgram Title: ANT 2023, revision BCPC Library link to program files:https://doi.org/10.17632/gr74wwckcp.1Developer's repository link: https://doi.org/10.5281/zenodo.10011563Licensing Provisions: Apache-2.0Programming language: Fortran 90Interfaces to other programs: For direct dynamics, the code has well tested interfaces to the Gaussian 09 [1], Gaussian 16 [2], MOPACmn [3], and Molpro [4] electronic structure codes. The interfaces are included, but these electronic structure programs must be obtained separately. Users may also provide their own interfaces to other electronic structure programs.[1] M. J. Frisch et al. Gaussian 09, Gaussian, Inc., Wallingford CT, 2016.[2] M. J. Frisch et al., Gaussian 16, Gaussian, Inc., Wallingford CT, 2016.[3] J. J. P. Stewart et al., MOPAC 5.022mn, University of Minnesota, Minneapolis, MN, 2015; Zenodo. https://doi.org/10.5281/zenodo.8153079[4] H.-J. Werner et al., J. Chem. Phys. 152 (2020) 144107.Nature of problem: classical, quasiclassical, or semiclassical molecular dynamics for electronically adiabatic or electronically nonadiabatic collisions and unimolecular processes of atoms, molecules, and clustersSolution method: The program integrates the classical or semiclassical equations of motion for the motion of the nuclei. ANT 2023 can use anharmonic initial-state selection for initial states of diatomics or harmonic initial-state selection for general polyatomics. The equations of motion for electronically adiabatic processes are Hamilton's equations with potential energy functions corresponding to the Born-Oppenheimer approximation. The equations of motion for electronically nonadiabatic processes (non-Born-Oppenheimer processes) include trajectory surface hopping (fewest switches with or without time uncertainty and with or without decoherence) or several possible mean-field methods, including the semiclassical Ehrenfest method (also called the time-dependent Hartree method), self-consistent decay of mixing, and coherent switching with decay of mixing. Electronically nonadiabatic processes may be treated using either the adiabatic representation or a diabatic representation, and the potential surfaces and couplings may be obtained from analytic fits in a user-supplied subroutine or by direct dynamics, which involves requesting energies, gradients, and couplings as needed from a quantum chemistry electronic structure program. In the adiabatic representation, the coupling may be nonadiabatic coupling vectors (based on gradients of electronic wave functions), time-derivative couplings (based on overlaps of electronic wave functions), or curvature-driven couplings (based on the curvatures of the adiabatic potential energy surfaces).Additional comments: The ANT 2023 program authors are Y. Shu, L. Zhang, J. Zheng, Z. H. Li, A. W. Jasper, D. A. Bonhommeau, R. Valero, R. Meana-Pañeda, S. L. Mielke, Z. Varga, and D. G. Truhlar [5]; the authors of the article [6] describing ANT 2023 are Y. Shu, L. Zhang, and D. G. Truhlar.

Exploring the excited state multi-proton transfer path and the associated photophysical properties of P-TNS molecule by DFT and TDDFT theory

Recently, Chen et al. designed and synthesized a new multi-purpose dye probe P-TNS with bifunctional groups, which has an ultra-fast excited state intramolecular proton transfer characteristic (ESIPT) (Spectrochim Acta A Mol Biomol Spectrosc., 2021, 262: 120084.). The P-TNS molecules are very sensitive to hydrazine (N2H4) and cyanide (CN-), which makes it have a good practical application prospect in the field of probe detection. However, the corresponding optical properties and the related mechanisms have not been systematically investigated in experiments. In the present work, the proton transfer pathways as well as the photophysical properties changes in the transfer path of P-TNS with three intramolecular hydrogen bonds (HB1, HB2 and HB3) are revealed for the first time. First, the analysis of potential energy surface and potential energy curve determined the stable conformation of P-TNS molecule and its isomer structure, and clarified the reaction mechanism of ESIPT process. Subsequently, the analysis of the frontier molecular orbitals reveal that the charge difference is the driving force required for the proton transfer process from the microscopic level, which led to the determination that the HB1 structure without the charge difference could not complete the ESIPT process. Finally, the variation of hydrogen bond strength and the path of proton transfer are demonstrated from several perspectives of hydrogen bond parameters, hydrogen bond energy, infrared vibrational frequency (IR) and reduced density gradient (RDG) surface. This study essentially explains the photophysical properties and proton transfer pathways of a new multipurpose dye probes for organic luminescence with bifunctional groups, which are important for the fields of spectroscopy and measurement technology, and also provides ideas for the design and synthesis of new fluorescent probes.

Formation of N(2D) from Hyperthermal Collisions between O(3P) and NO(X2Π).

Hyperthermal collisions between O(3P) and NO(X2Π) could lead to the formation of the first electronically excited atomic nitrogen (N(2D)), which plays a key role in plasma formation in shock-heated air. This process is facilitated mainly by four doublet states, and to a much lesser extent by two quartet states. In this work, we report quasi-classical trajectory studies of this reactive process using the four analytical adiabatic potential energy surfaces for the doublet states developed previously from fitting high-level ab initio data. The reactions were found to be strongly enhanced by vibrational excitation of the NO reactant, consistent with the existence of potential energy barriers in the exit channel. Despite the large endothermicity of the reaction, the rate coefficient is significant at high temperatures, suggesting a possible role of this reaction in the hyperthermal kinetics in the shock layer of a hypersonic (re)entry vehicle.

The CN(X 2Σ+) + C2H6 reaction: Dynamics study based on an analytical full-dimensional potential energy surface.

The hydrogen abstraction reaction of the cyano radical with molecules of ethane presents some interesting points in the chemistry from ultra-cold to combustion environments especially with regard to HCN(v) product vibrational distribution. In order to understand its dynamics, a new analytical full-dimensional potential energy surface was developed, named PES-2023. It uses a combination of valence bond and mechanic molecular terms as the functional form, fitted to high-level abinitio calculations at the explicitly correlated CCSD(T)-F12/aug-cc-pVTZ level on a reduced and selected number of points describing the reactive process. The new surface showed a continuous and smooth behavior, describing reasonably the topology of the reaction: high exothermicity, low barrier, and presence of intermediate complexes in the entrance and exit channels. Using quasi-classical trajectory calculations (QCT) on the new PES-2023, a dynamics study was performed at room temperature with special emphasis on the HCN(v1,v2,v3) product stretching and bending vibrational excitations, and the results were compared with the experimental evidence, which presented discrepancies in the bending excitation. The available energy was mostly deposited as HCN(v) vibrational energy with the vibrational population inverted in the CH stretching mode and not inverted in the CN stretching and bending modes, thus simulating the experimental evidence. Other dynamics properties at room temperature were also analyzed; cold rotational energy distribution was found, associated with a linear and soft transition state, and backward scattering distribution was found, associated with a rebound mechanism.

Trihydrogen Cation Helium Clusters: A New Potential Energy Surface.

We present a new analytical potential energy surface (PES) for the interaction between the trihydrogen cation and a He atom, , in its electronic ground state. The proposed PES has been built as a sum of two contributions: a polarization energy term due to the electric field generated by the molecular cation at the position of the polarizable He atom, and an exchange-repulsion and dispersion interactions represented by a sum of "atom-bond" potentials between the three bonds of and the He atom. All parameters of this new PES have been chosen and fitted from data obtained from high-level ab-initio calculations. Using this new PES plus the Aziz-Slaman potential for the interaction between Helium atoms and assuming pair-wise interactions, we carry out classical Basin-Hopping (BH) global optimization, semiclassical BH with Zero Point Energy corrections, and quantum Diffusion Monte Carlo simulations. We have found the minimum energy configurations of small He clusters doped with , , with N=1-16. The study of the energies of these clusters allows us to find a pronounced anomaly for N=12, in perfect agreement with previous experimental findings, which we relate to a greater relative stability of this aggregate.

Alternating Stereospecificity upon Central-Atom Change: Dynamics of the F- +PH2 Cl SN 2 Reaction Compared to its C- and N-Centered Analogues.

Central-atom effects on bimolecular nucleophilic substitution (SN 2) reactions are well-known in chemistry, however, the atomic-level SN 2 dynamics at phosphorous (P) centers has never been studied. We investigate the dynamics of the F- +PH2 Cl reaction with the quasi-classical trajectory method on a novel full-dimensional analytical potential energy surface fitted on high-level ab initio data. Our computations reveal intermediate dynamics compared to the F- +CH3 Cl and the F- +NH2 Cl SN 2 reactions: phosphorus as central atom leads to a more indirect SN 2 reaction with extensive complex-formation with respect to the carbon-centered one, however, the title reaction is more direct than its N-centered pair. Stereospecificity, characteristic at C-center, does not appear here either, due to the submerged front-side-attack retention path and the repeated entrance-channel inversional motion, whereas the multi-inversion mechanism discovered at nitrogen center is also undermined by the deep Walden-well. At low collision energies, 6 % of the PH2 F products form with retained configuration, mostly through complex-mediated mechanisms, while this ratio reaches 24 % at the highest energy due to the increasing dominance of the direct front-side mechanism and the smaller chance for hitting the deep Walden-inversion minimum. Our results suggest pronounced central-atom effects in SN 2 reactions, which can fundamentally change their (stereo)dynamics.

Partial Oxidation of Methane to Methanol by Using Molecular O2 on Pd2+ Catalyst: An Insight from Theory

AbstractThe partial oxidation of methane to methanol using cationic Pd2 dimers is investigated by employing density functional theory (DFT) method. We used B3PW91 functional for geometry optimization, and frequency calculations of all species involved in [Pd2]++O2+2CH4 reaction. Furthermore, a density‐fitting triple zeta valence with single‐polarization (def2TZVP) is used in the calculation to determine the atomic orbitals of the atoms. We oxidized Pd2+ to [Pd2O2]+ using O2 and performed possible partial oxidation of methane to methanol on [Pd2O2]+ and [Pd2O]+ and explored various intermediates and transition states on the potential energy surface (PES) diagram. From Potential Energy Surface (PES) analysis, it is found that the [Pd2O2]+ in doublet spin state multiplicity (SM=2) following radical mechanism is the more preferred pathway for methane to methanol conversion.

Vibrational Mode-Specific Dynamics of the OH + C2H6 Reaction.

We investigate the effects of the initial vibrational excitations on the dynamics of the OH + C2H6 → H2O + C2H5 reaction using the quasi-classical trajectory method and a full-dimensional analytical ab initio potential energy surface. Excitation of the initial CH, CC, and OH stretching modes enhances, slightly inhibits, and does not affect the reactivity, respectively. Translational energy activates the early-barrier title reaction more efficiently than OH and CC stretching excitations, in accord with the Polanyi rules whereas CH stretching modes have similar or higher efficacy than translation, showing that these rules are not always valid in polyatomic processes. Scattering angle, initial attack angle, and product translational energy distributions show the dominance of direct stripping with increasing collision energy, side-on OH and isotropic C2H6 attack preferences, and substantial reactant-product translational energy transfer without any significant mode specificity. The reactant vibrational excitation energy of OH and C2H6 flows into the H2O and C2H5 product vibrations, respectively, whereas product rotations are not affected. The computed mode-specific H2O vibrational distributions show that initial OH excitation appears in the asymmetric stretching vibration of the H2O product and allow comparison with experiments.

Structural, Spectroscopic, and Dynamic Properties of Li2+(X2∑g+) in Interaction with Krypton Atom.

We report a computational study of the potential energy surface (PES) and vibrational bound states for the ground electronic state of Li2+Kr. The PES was calculated in Jacobi coordinates at the Restricted Coupled Cluster method RCCSD(T) level of calculation and using aug-cc-pVnZ (n = 4 and 5) basis sets. Afterward, this PES is extrapolated to the complete basis set (CBS) limit for correction. The obtained interaction energies were, then, interpolated numerically using the reproducing kernel Hilbert space polynomial (RKHS) approach to produce analytic expressions for the 2D-PES. The analytical PES is used to solve the nuclear Schrodinger equation to determine the bound states' eigenvalues of Li2+Kr for a J = 0 total angular momentum configuration and to understand the effects of orientational anisotropy of the forces and the interplay between the repulsive and attractive interaction within the potential surface. In addition, the radial and angular distributions of some selected bound state levels, which lie below, around, and above the T-shaped 90° barrier well, are calculated and discussed. We note that the radial distributions clearly acquire a more complicated nodal structure and correspond to bending and stretching vibrational motions "mode" of the Kr atom along the radial coordinate, and the situation becomes very different at the highest bound states levels with energies higher than the T-shaped 90° barrier well. The shape of the distributions becomes even more complicated, with extended angular distributions and prominent differences between even and odd states.

Dynamics of C(3P) + OH(X 2Π) reaction on the new global HCO(X2A') potential energy surface.

A precise analytical potential energy surface (PES) of HCO(X2A') is fitted from a great quantity of abinitio energy points computed with the multi-reference configuration interaction method and aug-cc-pV(Q/5)Z basis sets. The whole energy points extrapolated to the complete basis set limit are fitted by the many-body expansion formula. The calculated topographic characteristics are analyzed and compared with the existing work to prove the precision of the present HCO(X2A') PES. By utilizing the time-dependent wave packet and quasi-classical trajectory methods, the reaction probabilities, integral cross sections, and rate constants are computed. The results are compared in detail with the former results carried out on the other PES. Moreover, the provided information on stereodynamics leads to an in-depth understanding of the role of collision energy in product distribution.

Exploring the versatile reactivity of the F- + SiH3Cl system on a full-dimensional coupled-cluster potential energy surface.

We develop a full-dimensional analytical potential energy surface (PES) for the F- + SiH3Cl reaction using Robosurfer for automatically sampling the configuration space, the robust [CCSD-F12b + BCCD(T) - BCCD]/aug-cc-pVTZ composite level of theory for computing the energy points, and the permutationally invariant polynomial method for fitting. Evolution of the fitting error and the percentage of the unphysical trajectories are monitored as a function of the iteration steps/number of energy points and polynomial order. Quasi-classical trajectory simulations on the new PES reveal rich dynamics resulting in high-probability SN2 (SiH3F + Cl-) and proton-transfer (SiH2Cl- + HF) products as well as several lower-probability channels, such as SiH2F- + HCl, SiH2FCl + H-, SiH2 + FHCl-, SiHFCl- + H2, SiHF + H2 + Cl-, and SiH2 + HF + Cl-. The Walden-inversion and front-side-attack-retention SN2 pathways are found to be competitive, producing nearly racemic products at high collision energies. The detailed atomic-level mechanisms of the various reaction pathways and channels as well as the accuracy of the analytical PES are analyzed along representative trajectories.

Dynamics of the Cl- + CH3I reaction on a high-level abinitio analytical potential energy surface.

We have developed a full-dimensional analytical abinitio potential energy surface (PES) for the Cl- + CH3I reaction using the Robosurfer program system. The energy points have been computed using a robust composite method defined as CCSD-F12b + BCCD(T) - BCCD with the aug-cc-pVTZ(-PP) basis set and have been fitted by the permutationally invariant polynomial approach. Quasi-classical trajectory simulations on the new PES reveal that two product channels are open in the collision energy (Ecoll) range of 1-80 kcal/mol, i.e., SN2 leading to I- + CH3Cl and iodine abstraction (above ∼45 kcal/mol) resulting in ICl- + CH3. Scattering angle, initial attack angle, product translational energy, and product internal energy distributions show that the SN2 reaction is indirect at low Ecoll and becomes direct-rebound-back-side (CH3-side) attack-type, as Ecoll increases. Iodine abstraction mainly proceeds with direct stripping mechanism with side-on/back-side attack preference. Comparison with crossed-beam experiments and previous direct dynamics simulations shows quantitative or qualitative agreement and also highlights possible theoretical and/or experimental issues motivating further research.