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Predissociation via conformational change: Photodissociation of N,N-dimethylnitrosamine in the S1 state


Nonella, M; Suter, H U; Huber, J R (2010). Predissociation via conformational change: Photodissociation of N,N-dimethylnitrosamine in the S1 state. Journal of Physical Chemistry. A, 114(50):13011-13015.

Abstract

We investigated the photodissociation mechanism of N,N-dimethylnitrosamine (CH3)2NNO (DMN) by ab
intio quantum chemical methods. Inspired by an earlier study we calculated two-dimensional potential energy
surfaces of the S1 state of DMN in its planar and pyramidal conformations. While the planar molecular geometry
appears to possess no direct dissociation channel, the pyramidal configuration is dissociative yielding the
products NO + (CH3)2N. Using wave packet dynamics on the planar S1 potential energy surface the
experimental absorption spectrum was well reproduced which gives indirect but strong support for the
nondissociative nature of this surface. The transition from the planar to the pyramidal conformation of DMN
was then investigated by an ab initio molecular dynamics method which revealed the time evolution of the
geometrical parameters of the molecule up to the dissociation of the N-N bond. This occurs about 90 fs after
photon excitation. The calculated minimum energy path along the N-N coordinate and the structural changes
of the molecule along this coordinate provided a detailed picture of this indirect dissociation or, more specific,
predissociation process via conformational change.

We investigated the photodissociation mechanism of N,N-dimethylnitrosamine (CH3)2NNO (DMN) by ab
intio quantum chemical methods. Inspired by an earlier study we calculated two-dimensional potential energy
surfaces of the S1 state of DMN in its planar and pyramidal conformations. While the planar molecular geometry
appears to possess no direct dissociation channel, the pyramidal configuration is dissociative yielding the
products NO + (CH3)2N. Using wave packet dynamics on the planar S1 potential energy surface the
experimental absorption spectrum was well reproduced which gives indirect but strong support for the
nondissociative nature of this surface. The transition from the planar to the pyramidal conformation of DMN
was then investigated by an ab initio molecular dynamics method which revealed the time evolution of the
geometrical parameters of the molecule up to the dissociation of the N-N bond. This occurs about 90 fs after
photon excitation. The calculated minimum energy path along the N-N coordinate and the structural changes
of the molecule along this coordinate provided a detailed picture of this indirect dissociation or, more specific,
predissociation process via conformational change.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2010
Deposited On:16 Feb 2011 18:17
Last Modified:05 Apr 2016 14:41
Publisher:American Chemical Society
ISSN:1089-5639
Publisher DOI:10.1021/jp107787j
PubMed ID:21090731
Permanent URL: http://doi.org/10.5167/uzh-44091

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