We present a quantum-mechanical theory to study excitation energy transfers between molecular systems in solution. The model is developed within the time-dependent (TD) density-functional theory and the solvent effects are introduced in terms of the polarizable continuum model (PCM). Unique characteristic of this model is that both ‘‘reaction field’’ and screening effects are included in a coherent and self-consistent way. This is obtained by introducing proper solvent-specific operators in the Kohn–Sham equations and in the corresponding TD scheme. The solvation model exploits the integral equation formalism ~IEF! version of PCM and it defines the solvent operators on a molecular cavity modeled on the real three-dimensional structure of the solute systems. Applications to EET in dimers of ethylene and naphtalene are presented and discussed.
Excitation energy transfer (EET) between molecules in condensed matter: a novel application of the Polarizable Continuum model (PCM)
MENNUCCI, BENEDETTA;TOMASI, IACOPO;
2004-01-01
Abstract
We present a quantum-mechanical theory to study excitation energy transfers between molecular systems in solution. The model is developed within the time-dependent (TD) density-functional theory and the solvent effects are introduced in terms of the polarizable continuum model (PCM). Unique characteristic of this model is that both ‘‘reaction field’’ and screening effects are included in a coherent and self-consistent way. This is obtained by introducing proper solvent-specific operators in the Kohn–Sham equations and in the corresponding TD scheme. The solvation model exploits the integral equation formalism ~IEF! version of PCM and it defines the solvent operators on a molecular cavity modeled on the real three-dimensional structure of the solute systems. Applications to EET in dimers of ethylene and naphtalene are presented and discussed.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
