Entropic effects in excited state CT reactions

Pigliucci, Anatolio; Vauthey, Eric; Rettig, W.

doi:10.1016/j.cplett.2008.12.091

Scientific article

English

Entropic effects in excited state CT reactions

Contributors

Pigliucci, Anatolio; Vauthey, Eric

; Rettig, W.

Published in

Chemical physics letters, vol. 469, no. 1, p. 115-120

Publication date

2009

Abstract

The kinetics of the dual fluorescence of several derivatives of dimethylaminobenzonitrile (DMABN) has been compared using fs-fluorescence upconversion experiments. Variation of the size and twist angle of the donor (dialkylamino group) suggest a large amplitude solvent-viscosity controlled diffusional twisting motion towards larger twist angles as the rate limiting step. Large rate differences were observed for an ester group as acceptor. Temperature dependent studies indicate that these differences are not connected with different activation barriers but with changes in the Arrhenius preexponential factor. It is argued that conical intersections along the reaction path can bring about these entropy changes.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Vauthey

Citation (ISO format)

PIGLIUCCI, Anatolio, VAUTHEY, Eric, RETTIG, W. Entropic effects in excited state CT reactions. In: Chemical physics letters, 2009, vol. 469, n° 1, p. 115–120. doi: 10.1016/j.cplett.2008.12.091

Article (Published version)

Identifiers

PID : unige:3557
DOI : 10.1016/j.cplett.2008.12.091

Additional URL for this publication

http://www.sciencedirect.com/science?_ob=MImg&_imagekey=B6TFN-4V82HP5-1-5&_cdi=5231&_user=779890&_orig=browse&_coverDate=02%2F03%2F2009&_sk=995309998&view=c&wchp=dGLbVzz-zSkWA&md5=bc9112ab8919e71511856d28bc936e86&ie=/sdarticle.pdf

Journal ISSN

0009-2614

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649downloads

Creation

02/10/2009 15:18:08

First validation

02/10/2009 15:18:08

Update

14/03/2023 15:15:20

Status update

14/03/2023 15:15:20

Last indexation

10/06/2025 21:29:52

Entropic effects in excited state CT reactions

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

Main files (1)

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Additional URL for this publication

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation