Quantum Scattering and Semiclassical Transition State Theory Calculations on Chemical Reactions of Polyatomic Molecules in Reduced Dimensions

Greene, Samuel M.; Xiao, Shan; Clary, David C.

doi:10.1002/9781119374978.ch4

Cited by 5 publications

(9 citation statements)

References 129 publications

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“…The approach has been used to test the accuracy of the SCTST for the same potential energy surfaces for a range of hydrogen atom transfer reactions of polyatomic molecules and the agreement between the two sets of results is excellent in every case. 4,16,17 Combining the RD approach with SCTST also produces a highly efficient theory that will be applicable to a very wide range of reactions of larger polyatomic molecules. 24 In this Feature Article we describe recent developments in the SCTST with particular emphasis on its application within the RD approach.…”

Section: This Theory Was Developed Bymentioning

confidence: 99%

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New Developments in Semiclassical Transition-State Theory

2019

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This Feature Article describes some recent developments and applications of the Semiclassical Transition State Theory (SCTST) for treating quantum tunnelling in chemical reactions. A reduced dimensional form of the SCTST is discussed and is shown to be particularly efficient as the required number of electronic structure calculations is reduced to an absolute minimum. We also describe how an alternative formulation of SCTST, called SCTST-θ, has advantages in allowing for straightforward applications of the SCTST for any form of the potential expansion at the transition state. We also illustrate the power of SCTST in applications to more complex systems. We show how polyatomic modes such as internal rotations and torsions can be treated efficiently in SCTST calculations. We also describe some applications of the method to hydrogen atom tunneling in unimolecular reactions including the degradation of chemical nerve agents and the decay of the atmospherically important Criegee intermediates.

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Section: This Theory Was Developed Bymentioning

confidence: 99%

“…Figure16. Some modes that correspond to relative translational and rotational modes in the reactant state.…”

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confidence: 99%

New Developments in Semiclassical Transition-State Theory

2019

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“…The first SCTST calculations of rate constants were done several years ago 108 when there were not good QRS computations for comparison and the method was not widely taken up. However, recent developments in ab initio quantum chemistry derivative codes and comparison with QRS calculations have demonstrated that SCTST is much more accurate than was realised previously 96,[110][111][112][113][114][115][116][117][118] .…”

Section: Rate Constantsmentioning

confidence: 96%

“…The RDQC approach has been useful in the testing of the accuracy of the SCTST. In every case considered to date [116][117][118]130 Also shown in both cases is the effective potential along the minimum energy path for both the QRS potential and the Eckart potential. It can be seen that the effective potential is very "Eckart-like" for the region of the minimum energy path close to the transition state.…”

Section: Rate Constantsmentioning

confidence: 99%

Spiers Memorial Lecture : Introductory lecture: quantum dynamics of chemical reactions

Clary

2018

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“…Such complexity is usually over‐simplified by reducing the PES to a number of “connected” stationary points making up a one‐dimensional diagram accounting for most of the involved chemistry. On the other hand, modeling and interpreting spectroscopic and dynamical features of a molecular system requires the analysis of the PES as a function of at least a few degrees of freedom, typically those that are mostly involved in the physical process of interest . A useful approach in this respect is that of opportunely reducing the dimensionality of the PES to two coordinates and build a three‐dimensional representation where the selected coordinates are used as the latitude and the longitude and the associated value of the PES as the elevation.…”

Section: Introductionmentioning

confidence: 99%

Chemical promenades: Exploring potential‐energy surfaces with immersive virtual reality

et al. 2020

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The virtual-reality framework AVATAR (Advanced Virtual Approach to Topological Analysis of Reactivity) for the immersive exploration of potential-energy landscapes is presented. AVATAR is based on modern consumer-grade virtual-reality technology and builds on two key concepts: (a) the reduction of the dimensionality of the potential-energy surface to two process-tailored, physically meaningful generalized coordinates, and (b) the analogy between the evolution of a chemical process and a pathway through valleys (potential wells) and mountain passes (saddle points) of the associated potential energy landscape. Examples including the discovery of competitive reaction paths in simple A + BC collisional systems and the interconversion between conformers in ring-puckering motions of flexible rings highlight the innovation potential that augmented and virtual reality convey for teaching, training, and supporting research in chemistry. K E Y W O R D S atom diatom reactions, immersive virtual reality, potential energy surface, ring puckering motions 1 | INTRODUCTION As well known, rigorous simulations of molecular processes should be based on the solution of the Schrödinger equation for the wavefunction of the involved nuclei and electrons, which is usually cast in its nonrelativistic time-independent form with a Hamiltonian including a kinetic term for the electronsT e , a kinetic term for the nucleiT N , and an interaction-potential term V (r, R), with r and R being the set of spatial coordinates of electrons and nuclei, respectively.This equation is seldom solved as is, due to the associated mathematical difficulties and computational cost. More commonly, on the grounds that the nuclei are much heavier than the electrons, the Born-Oppenheimer approximation [1] is adopted and the problem is broken down in two separate problems, one for the motion of the electrons at a given nuclear geometry:T

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Quantum Scattering and Semiclassical Transition State Theory Calculations on Chemical Reactions of Polyatomic Molecules in Reduced Dimensions

Cited by 5 publications

References 129 publications

New Developments in Semiclassical Transition-State Theory

New Developments in Semiclassical Transition-State Theory

Spiers Memorial Lecture : Introductory lecture: quantum dynamics of chemical reactions

Chemical promenades: Exploring potential‐energy surfaces with immersive virtual reality

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