Molecular Photofragmentation Dynamics in the Gas and Condensed Phases

Exciting a molecule with an ultraviolet photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gas-phase molecule can be viewed as a closed system: Energy and momentum are conserved, and the...

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Bibliographic Details
Published in:Annual review of physical chemistry 2017-05, Vol.68 (1), p.63-82
Main Authors: Ashfold, Michael N.R, Murdock, Daniel, Oliver, Thomas A.A
Format: Article
Language:English
Subjects:
Condensation
conical intersections
Dissipation
Energy
Energy conservation
Energy of dissociation
Fission
Gases
Molecules
nonadiabatic dynamics
Photochemistry
Photodissociation
Photoexcitation
photoinduced ring opening
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Summary:Exciting a molecule with an ultraviolet photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gas-phase molecule can be viewed as a closed system: Energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process. Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission and will dissipate any excess energy partitioned into the dissociation products. Products that have no analog in the corresponding gas-phase study may arise by, for example, geminate recombination. Here, we illustrate the extent to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.
ISSN:0066-426X
1545-1593
DOI:10.1146/annurev-physchem-052516-050756