A three-dimensional quantum reactive scattering study of the I + di reaction and of the IDI- photodetachment spectrum

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

In this paper are presented the results of a coupled-channel hyperspherical reactive scattering calculation of bimolecular reaction probabilities for the I + DI → ID + I reaction and of Franck-Condon factors for the photodetachment of IDI-. The calculation is fully three-dimensional, but only the J = 0 partial wave is considered. The results show significant contributions of both resonances and direct scattering to the reaction dynamics. Very narrow resonances associated with transition-state quantum numbers (ν1, ν2, ν3) = (000) and (100) are found and these are in excellent agreement with bound-state calculations by Clary and Connor. Much broader excited-state resonances labelled by the quantum numbers (002), (102), (202), (302), (004), (104), (204) and (304) have also been located. The calculated photodetachment spectra show that these broad resonances play a dominant role in determining two peaks that have recently been observed experimentally by Neumark and co-workers. The narrow resonances (000) and (100) are, by contrast, overwhelmed by direct scattering threshold contributions in determining a third peak in the photodetachment spectrum. An 'extra' peak also appears in the calculated photodetachment spectrum that is not seen in the experiments. This peak is due to the direct reaction threshold for the I + DI(v = 1) reaction, and presumably it arises because of inaccuracies in our potential surface. Its importance should therefore provide a useful diagnostic for improvements to the surface.

Original languageEnglish
Pages (from-to)1729-1735
Number of pages7
JournalJournal of the Chemical Society - Faraday Transactions
Volume86
Issue number10
DOIs
Publication statusPublished - 1990

Fingerprint

photodetachment
Scattering
scattering
quantum numbers
thresholds
Excited states
excitation
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{2bf711966ff94d41a80ff93fb0564044,
title = "A three-dimensional quantum reactive scattering study of the I + di reaction and of the IDI- photodetachment spectrum",
abstract = "In this paper are presented the results of a coupled-channel hyperspherical reactive scattering calculation of bimolecular reaction probabilities for the I + DI → ID + I reaction and of Franck-Condon factors for the photodetachment of IDI-. The calculation is fully three-dimensional, but only the J = 0 partial wave is considered. The results show significant contributions of both resonances and direct scattering to the reaction dynamics. Very narrow resonances associated with transition-state quantum numbers (ν1, ν2, ν3) = (000) and (100) are found and these are in excellent agreement with bound-state calculations by Clary and Connor. Much broader excited-state resonances labelled by the quantum numbers (002), (102), (202), (302), (004), (104), (204) and (304) have also been located. The calculated photodetachment spectra show that these broad resonances play a dominant role in determining two peaks that have recently been observed experimentally by Neumark and co-workers. The narrow resonances (000) and (100) are, by contrast, overwhelmed by direct scattering threshold contributions in determining a third peak in the photodetachment spectrum. An 'extra' peak also appears in the calculated photodetachment spectrum that is not seen in the experiments. This peak is due to the direct reaction threshold for the I + DI(v = 1) reaction, and presumably it arises because of inaccuracies in our potential surface. Its importance should therefore provide a useful diagnostic for improvements to the surface.",
author = "Schatz, {George C}",
year = "1990",
doi = "10.1039/FT9908601729",
language = "English",
volume = "86",
pages = "1729--1735",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "10",

}

TY - JOUR

T1 - A three-dimensional quantum reactive scattering study of the I + di reaction and of the IDI- photodetachment spectrum

AU - Schatz, George C

PY - 1990

Y1 - 1990

N2 - In this paper are presented the results of a coupled-channel hyperspherical reactive scattering calculation of bimolecular reaction probabilities for the I + DI → ID + I reaction and of Franck-Condon factors for the photodetachment of IDI-. The calculation is fully three-dimensional, but only the J = 0 partial wave is considered. The results show significant contributions of both resonances and direct scattering to the reaction dynamics. Very narrow resonances associated with transition-state quantum numbers (ν1, ν2, ν3) = (000) and (100) are found and these are in excellent agreement with bound-state calculations by Clary and Connor. Much broader excited-state resonances labelled by the quantum numbers (002), (102), (202), (302), (004), (104), (204) and (304) have also been located. The calculated photodetachment spectra show that these broad resonances play a dominant role in determining two peaks that have recently been observed experimentally by Neumark and co-workers. The narrow resonances (000) and (100) are, by contrast, overwhelmed by direct scattering threshold contributions in determining a third peak in the photodetachment spectrum. An 'extra' peak also appears in the calculated photodetachment spectrum that is not seen in the experiments. This peak is due to the direct reaction threshold for the I + DI(v = 1) reaction, and presumably it arises because of inaccuracies in our potential surface. Its importance should therefore provide a useful diagnostic for improvements to the surface.

AB - In this paper are presented the results of a coupled-channel hyperspherical reactive scattering calculation of bimolecular reaction probabilities for the I + DI → ID + I reaction and of Franck-Condon factors for the photodetachment of IDI-. The calculation is fully three-dimensional, but only the J = 0 partial wave is considered. The results show significant contributions of both resonances and direct scattering to the reaction dynamics. Very narrow resonances associated with transition-state quantum numbers (ν1, ν2, ν3) = (000) and (100) are found and these are in excellent agreement with bound-state calculations by Clary and Connor. Much broader excited-state resonances labelled by the quantum numbers (002), (102), (202), (302), (004), (104), (204) and (304) have also been located. The calculated photodetachment spectra show that these broad resonances play a dominant role in determining two peaks that have recently been observed experimentally by Neumark and co-workers. The narrow resonances (000) and (100) are, by contrast, overwhelmed by direct scattering threshold contributions in determining a third peak in the photodetachment spectrum. An 'extra' peak also appears in the calculated photodetachment spectrum that is not seen in the experiments. This peak is due to the direct reaction threshold for the I + DI(v = 1) reaction, and presumably it arises because of inaccuracies in our potential surface. Its importance should therefore provide a useful diagnostic for improvements to the surface.

UR - http://www.scopus.com/inward/record.url?scp=0003392133&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0003392133&partnerID=8YFLogxK

U2 - 10.1039/FT9908601729

DO - 10.1039/FT9908601729

M3 - Article

VL - 86

SP - 1729

EP - 1735

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 10

ER -