Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants
Abstract
One of the outstanding issues in the quantum instanton (QI) theory (or any transition statetype theory) for thermal rate constants of chemical reactions is the choice of an appropriate ''dividing surface'' (DS) that separates reactants and products. (In the general version of the QI theory, there are actually two dividing surfaces involved.) This paper shows one simple and general way for choosing DS's for use in QI Theory, namely using the family of (hyper) planes normal to the minimum energy path (MEP) on the potential energy surface at various distances s along it. Here the reaction coordinate is not one of the dynamical coordinates of the system (which will in general be the Cartesian coordinates of the atoms), but rather simply a parameter which specifies the DS. It is also shown how this idea can be implemented for an Natom system in 3d space in a way that preserves overall translational and rotational invariance. Numerical application to a simple system (the colliner H + H{sub 2} reaction) is presented to illustrate the procedure.
 Authors:
 Publication Date:
 Research Org.:
 Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
 Sponsoring Org.:
 USDOE Director. Office of Science. Office of Basic EnergySciences; US Office of Defense. Office of Naval Research Grant#N000140110236
 OSTI Identifier:
 891631
 Report Number(s):
 LBNL59735
Journal ID: ISSN 00219606; JCPSA6; R&D Project: 401501; BnR: KC0301020; TRN: US0605454
 DOE Contract Number:
 DEAC0205CH11231
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Journal of Chemical Physics; Journal Volume: 125; Related Information: Journal Publication Date: 2006
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; ATOMS; CARTESIAN COORDINATES; CHEMICAL REACTIONS; INSTANTONS; POTENTIAL ENERGY; ROTATIONAL INVARIANCE
Citation Formats
Li, Yimin, and Miller, Wlliam H. Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants. United States: N. p., 2006.
Web.
Li, Yimin, & Miller, Wlliam H. Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants. United States.
Li, Yimin, and Miller, Wlliam H. Wed .
"Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants". United States.
doi:. https://www.osti.gov/servlets/purl/891631.
@article{osti_891631,
title = {Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants},
author = {Li, Yimin and Miller, Wlliam H.},
abstractNote = {One of the outstanding issues in the quantum instanton (QI) theory (or any transition statetype theory) for thermal rate constants of chemical reactions is the choice of an appropriate ''dividing surface'' (DS) that separates reactants and products. (In the general version of the QI theory, there are actually two dividing surfaces involved.) This paper shows one simple and general way for choosing DS's for use in QI Theory, namely using the family of (hyper) planes normal to the minimum energy path (MEP) on the potential energy surface at various distances s along it. Here the reaction coordinate is not one of the dynamical coordinates of the system (which will in general be the Cartesian coordinates of the atoms), but rather simply a parameter which specifies the DS. It is also shown how this idea can be implemented for an Natom system in 3d space in a way that preserves overall translational and rotational invariance. Numerical application to a simple system (the colliner H + H{sub 2} reaction) is presented to illustrate the procedure.},
doi = {},
journal = {Journal of Chemical Physics},
number = ,
volume = 125,
place = {United States},
year = {Wed Feb 22 00:00:00 EST 2006},
month = {Wed Feb 22 00:00:00 EST 2006}
}

No abstract prepared.

A comparative study of the quantum dynamics and rate constants of the O({sup 3}P) + HC1 reaction described by two potential surfaces.
Wave packet calculations, using direct and dampedL{sup 2} real propagation methods, of initial stateresolved and cumulative reaction probabilities for the O({sup 3}P) + HCl({sup 1}{Sigma}{sup +}){yields}OH({sup 2}{Pi}) + Cl({sup 2}P) reaction are reported. Results are obtained using the recently developed 'S4' potential surface of Ramachandran and coworkers and, for comparison, the earlier Koizumi, Schatz, and Gordon (KSG) potential energy surface. Most calculations are for total angular momentum J = 0, although some J>0 centrifugal sudden results are also obtained. The thermal rate constant and the rate constant for HCl({nu} = 1) are obtained from the J = 0 cumulative reactionmore »