Electronic Predissociation in the Dichloromethane Cation CH2Cl2+ Electronic State (2)A(1)

Allan Christian Petersen; Mads Koerstz; Kurt, V Mikkelsen; Theis, I Solling

doi:10.1021/acs.jpca.9b02022

Electronic Predissociation in the Dichloromethane Cation CH2Cl2+ Electronic State (2)A(1)

Allan Christian Petersen, Mads Koerstz, Kurt, V Mikkelsen, Theis, I Solling

1 Citationer (Scopus)

Abstract

The loss of a Cl atom from metastable CH ₂ Cl ₂ ⁺ in the mass-analyzed ion kinetic energy experiment is characterized by a borderline zero kinetic energy release and large kinetic isotope effects on chlorine and hydrogen. Ab initio calculations are employed to assist the interpretation in terms of a nonadiabatic reaction involving electronic predissociation of the electronically excited state ² A ₁ and two-dimensional reaction dynamics. Strong curvature in the reaction coordinate leads to a bobsled effect that accounts for the low kinetic energy release. The kinetic isotope effects enter via the predissociation rate and are interpreted in terms of vibrational overlap integrals.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry A
Vol/bind	123
Udgave nummer	18
Sider (fra-til)	4048-4056
ISSN	1089-5639
DOI	https://doi.org/10.1021/acs.jpca.9b02022
Status	Udgivet - 9 maj 2019

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10.1021/acs.jpca.9b02022

Citationsformater

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title = "Electronic Predissociation in the Dichloromethane Cation CH2Cl2+ Electronic State (2)A(1)",

abstract = " The loss of a Cl atom from metastable CH 2 Cl 2 + in the mass-analyzed ion kinetic energy experiment is characterized by a borderline zero kinetic energy release and large kinetic isotope effects on chlorine and hydrogen. Ab initio calculations are employed to assist the interpretation in terms of a nonadiabatic reaction involving electronic predissociation of the electronically excited state 2 A 1 and two-dimensional reaction dynamics. Strong curvature in the reaction coordinate leads to a bobsled effect that accounts for the low kinetic energy release. The kinetic isotope effects enter via the predissociation rate and are interpreted in terms of vibrational overlap integrals. ",

author = "Petersen, {Allan Christian} and Mads Koerstz and Mikkelsen, {Kurt, V} and Solling, {Theis, I}",

year = "2019",

month = may,

day = "9",

doi = "10.1021/acs.jpca.9b02022",

language = "English",

volume = "123",

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T1 - Electronic Predissociation in the Dichloromethane Cation CH2Cl2+ Electronic State (2)A(1)

AU - Petersen, Allan Christian

AU - Koerstz, Mads

AU - Mikkelsen, Kurt, V

AU - Solling, Theis, I

PY - 2019/5/9

Y1 - 2019/5/9

N2 - The loss of a Cl atom from metastable CH 2 Cl 2 + in the mass-analyzed ion kinetic energy experiment is characterized by a borderline zero kinetic energy release and large kinetic isotope effects on chlorine and hydrogen. Ab initio calculations are employed to assist the interpretation in terms of a nonadiabatic reaction involving electronic predissociation of the electronically excited state 2 A 1 and two-dimensional reaction dynamics. Strong curvature in the reaction coordinate leads to a bobsled effect that accounts for the low kinetic energy release. The kinetic isotope effects enter via the predissociation rate and are interpreted in terms of vibrational overlap integrals.

AB - The loss of a Cl atom from metastable CH 2 Cl 2 + in the mass-analyzed ion kinetic energy experiment is characterized by a borderline zero kinetic energy release and large kinetic isotope effects on chlorine and hydrogen. Ab initio calculations are employed to assist the interpretation in terms of a nonadiabatic reaction involving electronic predissociation of the electronically excited state 2 A 1 and two-dimensional reaction dynamics. Strong curvature in the reaction coordinate leads to a bobsled effect that accounts for the low kinetic energy release. The kinetic isotope effects enter via the predissociation rate and are interpreted in terms of vibrational overlap integrals.

U2 - 10.1021/acs.jpca.9b02022

DO - 10.1021/acs.jpca.9b02022

M3 - Journal article

C2 - 30986053

SN - 1089-5639

VL - 123

SP - 4048

EP - 4056

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 18

ER -

Electronic Predissociation in the Dichloromethane Cation CH2Cl2+ Electronic State (2)A(1)

Abstract

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