Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD, and D + FH

George C Schatz, Aron Kuppermann

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30 Citations (Scopus)

Abstract

We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(υ), D + FD(υ), H + FD(υ), and D + FH(υ) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number υ and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(υ) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with υ→υ - 1 processes dominating.

Original languageEnglish
Pages (from-to)2737-2743
Number of pages7
JournalJournal of Chemical Physics
Volume72
Issue number4
Publication statusPublished - 1980

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deactivation
Rate constants
Potential energy surfaces
transition probabilities
collisions
deuterium fluorides
Trajectories
Atoms
vibrational states
quantum numbers
reagents
Chemical analysis
potential energy
trajectories
atoms

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD, and D + FH",
abstract = "We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(υ), D + FD(υ), H + FD(υ), and D + FH(υ) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number υ and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(υ) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with υ→υ - 1 processes dominating.",
author = "Schatz, {George C} and Aron Kuppermann",
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T2 - An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD, and D + FH

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AU - Kuppermann, Aron

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N2 - We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(υ), D + FD(υ), H + FD(υ), and D + FH(υ) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number υ and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(υ) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with υ→υ - 1 processes dominating.

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