New semiempirical method of modeling potential energy surfaces for generalized TST and application to the kinetic isotope effects in the CI-H-H system

Bruce C. Garrett, Donald G. Truhlar, Alan W. Magnuson

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

We present a test of bond-energy-bond-order (BEBO)-type potential energy surfaces for the Cl-H-H reaction system. We consider two methods, the rotated-Morse BEBO (RMBEBO) method and the Agmon-Levine-plus-anti-Morse bend (AL/AB) method. Each method is treated as a one-parameter semiempirical method. The parameter is adjusted to the energy of activation for Cl+H2 and the test of the method is the comparison of predicted kinetic isotope effects (KIE's) to experiment. Dynamical calculations are carried out by the improved canonical variational transition state theory with Marcus-Coltrin-path semiclassical adiabatic ground-state transmission coefficients as well as with simpler methods. The RMBEBO surfaces are not successful, but the AL/AB method is as successful as previously employed two-parameter methods. The anti-Morse-bend approximation is a general procedure, and it is tested successfully against ab initio calculations.

Original languageEnglish (US)
Pages (from-to)2321-2331
Number of pages11
JournalThe Journal of chemical physics
Volume76
Issue number5
DOIs
StatePublished - Jan 1 1982

Fingerprint

Potential energy surfaces
Isotopes
isotope effect
potential energy
Kinetics
kinetics
Ground state
Chemical activation
energy
activation
ground state
Experiments
coefficients
approximation

Cite this

New semiempirical method of modeling potential energy surfaces for generalized TST and application to the kinetic isotope effects in the CI-H-H system. / Garrett, Bruce C.; Truhlar, Donald G.; Magnuson, Alan W.

In: The Journal of chemical physics, Vol. 76, No. 5, 01.01.1982, p. 2321-2331.

Research output: Contribution to journalArticle

@article{82d820716ddf4eb0b3559b844132f7db,
title = "New semiempirical method of modeling potential energy surfaces for generalized TST and application to the kinetic isotope effects in the CI-H-H system",
abstract = "We present a test of bond-energy-bond-order (BEBO)-type potential energy surfaces for the Cl-H-H reaction system. We consider two methods, the rotated-Morse BEBO (RMBEBO) method and the Agmon-Levine-plus-anti-Morse bend (AL/AB) method. Each method is treated as a one-parameter semiempirical method. The parameter is adjusted to the energy of activation for Cl+H2 and the test of the method is the comparison of predicted kinetic isotope effects (KIE's) to experiment. Dynamical calculations are carried out by the improved canonical variational transition state theory with Marcus-Coltrin-path semiclassical adiabatic ground-state transmission coefficients as well as with simpler methods. The RMBEBO surfaces are not successful, but the AL/AB method is as successful as previously employed two-parameter methods. The anti-Morse-bend approximation is a general procedure, and it is tested successfully against ab initio calculations.",
author = "Garrett, {Bruce C.} and Truhlar, {Donald G.} and Magnuson, {Alan W.}",
year = "1982",
month = "1",
day = "1",
doi = "10.1063/1.443304",
language = "English (US)",
volume = "76",
pages = "2321--2331",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "5",

}

TY - JOUR

T1 - New semiempirical method of modeling potential energy surfaces for generalized TST and application to the kinetic isotope effects in the CI-H-H system

AU - Garrett, Bruce C.

AU - Truhlar, Donald G.

AU - Magnuson, Alan W.

PY - 1982/1/1

Y1 - 1982/1/1

N2 - We present a test of bond-energy-bond-order (BEBO)-type potential energy surfaces for the Cl-H-H reaction system. We consider two methods, the rotated-Morse BEBO (RMBEBO) method and the Agmon-Levine-plus-anti-Morse bend (AL/AB) method. Each method is treated as a one-parameter semiempirical method. The parameter is adjusted to the energy of activation for Cl+H2 and the test of the method is the comparison of predicted kinetic isotope effects (KIE's) to experiment. Dynamical calculations are carried out by the improved canonical variational transition state theory with Marcus-Coltrin-path semiclassical adiabatic ground-state transmission coefficients as well as with simpler methods. The RMBEBO surfaces are not successful, but the AL/AB method is as successful as previously employed two-parameter methods. The anti-Morse-bend approximation is a general procedure, and it is tested successfully against ab initio calculations.

AB - We present a test of bond-energy-bond-order (BEBO)-type potential energy surfaces for the Cl-H-H reaction system. We consider two methods, the rotated-Morse BEBO (RMBEBO) method and the Agmon-Levine-plus-anti-Morse bend (AL/AB) method. Each method is treated as a one-parameter semiempirical method. The parameter is adjusted to the energy of activation for Cl+H2 and the test of the method is the comparison of predicted kinetic isotope effects (KIE's) to experiment. Dynamical calculations are carried out by the improved canonical variational transition state theory with Marcus-Coltrin-path semiclassical adiabatic ground-state transmission coefficients as well as with simpler methods. The RMBEBO surfaces are not successful, but the AL/AB method is as successful as previously employed two-parameter methods. The anti-Morse-bend approximation is a general procedure, and it is tested successfully against ab initio calculations.

UR - http://www.scopus.com/inward/record.url?scp=36749108696&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36749108696&partnerID=8YFLogxK

U2 - 10.1063/1.443304

DO - 10.1063/1.443304

M3 - Article

AN - SCOPUS:36749108696

VL - 76

SP - 2321

EP - 2331

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 5

ER -