Electronic Predissociation in the Dichloromethane Cation CH                         2                         Cl                         2                         +                          Electronic State                          2                         A                         1

Allan Christian Petersen; Mads Koerstz; Kurt V. Mikkelsen; Theis I. Sølling

doi:10.1021/acs.jpca.9b02022

Electronic Predissociation in the Dichloromethane Cation CH ₂ Cl ₂ ⁺ Electronic State ² A ₁

Allan Christian Petersen
, Mads Koerstz
, Kurt V. Mikkelsen
, Theis I. Sølling

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

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.

Original language	English
Pages (from-to)	4048-4056
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	123
Issue number	18
DOIs	https://doi.org/10.1021/acs.jpca.9b02022
State	Published - 9 May 2019
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2019 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry

Access to Document

10.1021/acs.jpca.9b02022

Cite this

Petersen, A. C., Koerstz, M., Mikkelsen, K. V., & Sølling, T. I. (2019). Electronic Predissociation in the Dichloromethane Cation CH ₂ Cl ₂ ⁺ Electronic State ² A ₁ Journal of Physical Chemistry A, 123(18), 4048-4056. https://doi.org/10.1021/acs.jpca.9b02022

Petersen, Allan Christian ; Koerstz, Mads ; Mikkelsen, Kurt V. et al. / Electronic Predissociation in the Dichloromethane Cation CH ₂ Cl ₂ ⁺ Electronic State ² A ₁ In: Journal of Physical Chemistry A. 2019 ; Vol. 123, No. 18. pp. 4048-4056.

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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.",

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Petersen, AC, Koerstz, M, Mikkelsen, KV & Sølling, TI 2019, ' Electronic Predissociation in the Dichloromethane Cation CH ₂ Cl ₂ ⁺ Electronic State ² A ₁ ', Journal of Physical Chemistry A, vol. 123, no. 18, pp. 4048-4056. https://doi.org/10.1021/acs.jpca.9b02022

Electronic Predissociation in the Dichloromethane Cation CH ₂ Cl ₂ ⁺ Electronic State ² A ₁ . / Petersen, Allan Christian; Koerstz, Mads; Mikkelsen, Kurt V. et al.
In: Journal of Physical Chemistry A, Vol. 123, No. 18, 09.05.2019, p. 4048-4056.

Research output: Contribution to journal › Article › peer-review

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AU - Sølling, Theis I.

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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.

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Petersen AC, Koerstz M, Mikkelsen KV, Sølling TI. Electronic Predissociation in the Dichloromethane Cation CH ₂ Cl ₂ ⁺ Electronic State ² A ₁ Journal of Physical Chemistry A. 2019 May 9;123(18):4048-4056. doi: 10.1021/acs.jpca.9b02022