We review the field of computational studies of photochemistry in condensed phases, with particular emphasis on the nonadiabatic dynamics of excited states. We examine methods for the determination of potential energy surfaces (PES) and other electronic properties in large systems, from clusters to liquids and crystals. The change of the PES with respect to the isolated molecule case is the most important item of the "static" environmental effects in photochemistry. "Dynamic" effects mainly consist in the transfer of energy and momentum from the chromophore or reactive center to the surrounding molecules. The interplay of internal processes, including the photoreaction, with thermalization and other more specific effects of chemical environment, can hardly be analyzed without the help of simulations of the excited state dynamics. A survey of methods and applications shows advantages and weaknesses of the basic choices offered by the state of the art: quantum wavepacket versus trajectory approaches, direct versus two-step dynamics, continuum versus explicit representations of the solvent.
Photochemistry in condensed phase
GRANUCCI, GIOVANNI;PERSICO, MAURIZIO
2007-01-01
Abstract
We review the field of computational studies of photochemistry in condensed phases, with particular emphasis on the nonadiabatic dynamics of excited states. We examine methods for the determination of potential energy surfaces (PES) and other electronic properties in large systems, from clusters to liquids and crystals. The change of the PES with respect to the isolated molecule case is the most important item of the "static" environmental effects in photochemistry. "Dynamic" effects mainly consist in the transfer of energy and momentum from the chromophore or reactive center to the surrounding molecules. The interplay of internal processes, including the photoreaction, with thermalization and other more specific effects of chemical environment, can hardly be analyzed without the help of simulations of the excited state dynamics. A survey of methods and applications shows advantages and weaknesses of the basic choices offered by the state of the art: quantum wavepacket versus trajectory approaches, direct versus two-step dynamics, continuum versus explicit representations of the solvent.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
