We develop an extension of the infinite swapping and partial infinite swapping techniques [N. Plattner, J. D. Doll, P. Dupuis, H. Wang, Y. Liu, and J. E. Gubernatis, J. Chem. Phys. 135, 134111 (2011)] to curved spaces. Furthermore, we test the performance of infinite swapping and partial infinite swapping in a series of flat spaces characterized by the same potential energy surface model. We de...

An energy-based method is proposed for the diabatization of the OH(2Pi)+F(2P)-->O(3P)+HF(1Sigma+) reaction. It is demonstrated that the diabatic representation obtained is regularized, i.e., the residual derivative couplings do not present singularities at the conical intersections appearing along the reaction path. This method only requires the knowledge of the 1,2 3A" and 1 3A' eigenvalues an...

The Huggins band of ozone is investigated by means of dynamics calculations using a new (diabatic) potential energy surface for the 3 (1)A'(1B2) state. The good overall agreement of the calculated spectrum of vibrational energies and intensities with the experimental spectrum, especially at low to intermediate excitation energies, is considered as evidence that the Huggins band is due to the tw...

A method for interpolating molecular potential energy surfaces introduced [Ischtwan and Collins, J. Chem. Phys. 100, 8080 (1994)] and developed as an iterative scheme has been improved by different criteria for the selection of the data points. Refinements in the selection procedure are based on the variance of the interpolation and the direct exploration of the interpolation error, and produce...

Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical va...

A generalization of the coupled cluster (CC) singles, doubles, and a hybrid treatment of connected triples [denoted as CCSD(T)-h] [Shen et al., J. Chem. Phys. 132, 114115 (2010)] to the restricted Hartree-Fock (RHF) reference is presented. In this approach, active (or pseudoactive) RHF orbitals are constructed automatically by performing unitary transformations of canonical RHF orbitals so that...

The possible existence of a complex-forming pathway for the H+O(2) reaction has been investigated by means of both quantum mechanical and statistical techniques. Reaction probabilities, integral cross sections, and differential cross sections have been obtained with a statistical quantum method and the mean potential phase space theory. The statistical predictions are compared to exact results ...

The H(+) + D(2) --> HD + D(+) reaction has been theoretically investigated by means of an exact quantum mechanical approach, a quasiclassical trajectory method, and two statistical methods based in the propagation of either wave functions or trajectories. The study addresses the possible changes on the overall dynamics of the title reaction when the D(2) diatom is rotationally excited to its v ...

Motivated by a recent experiment [H. Pan and K. Liu, J. Chem. Phys. 140, 191101 (2014)], we report a quasiclassical trajectory study of the O((3)P) + CH4(vk = 0, 1) → OH + CH3 [k = 1 and 3] reactions on an ab initio potential energy surface. The computed angular distributions and cross sections correlated to the OH(v = 0, 1) + CH3(v = 0) coincident product states can be directly compared to exp...

The dynamics of the singlet channel of the Si+O(2)-->SiO+O reaction is investigated by means of quasiclassical trajectory (QCT) calculations and two statistical based methods, the statistical quantum method (SQM) and a semiclassical version of phase space theory (PST). The dynamics calculations have been performed on the ground (1)A(') potential energy surface of Dayou and Spielfiedel [J. Chem....