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

TY - JOUR

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 A

JF - Journal of Physical Chemistry A

IS - 18

ER -