| Autor: |
Nelson TR; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States., White AJ; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States., Bjorgaard JA; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States., Sifain AE; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States.; U.S. Army Research Laboratory , Aberdeen Proving Ground , Maryland 21005 , United States., Zhang Y; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States., Nebgen B; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States., Fernandez-Alberti S; Universidad Nacional de Quilmes/CONICET , Roque Saenz Peña 352 , B1876BXD Bernal , Argentina., Mozyrsky D; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States., Roitberg AE; Department of Chemistry , University of Florida , Gainesville , Florida 32611 , United States., Tretiak S; Theoretical Division , Los Alamos National Laboratory , Los Alamos , New Mexico 87545 , United States. |
| Abstrakt: |
Optically active molecular materials, such as organic conjugated polymers and biological systems, are characterized by strong coupling between electronic and vibrational degrees of freedom. Typically, simulations must go beyond the Born-Oppenheimer approximation to account for non-adiabatic coupling between excited states. Indeed, non-adiabatic dynamics is commonly associated with exciton dynamics and photophysics involving charge and energy transfer, as well as exciton dissociation and charge recombination. Understanding the photoinduced dynamics in such materials is vital to providing an accurate description of exciton formation, evolution, and decay. This interdisciplinary field has matured significantly over the past decades. Formulation of new theoretical frameworks, development of more efficient and accurate computational algorithms, and evolution of high-performance computer hardware has extended these simulations to very large molecular systems with hundreds of atoms, including numerous studies of organic semiconductors and biomolecules. In this Review, we will describe recent theoretical advances including treatment of electronic decoherence in surface-hopping methods, the role of solvent effects, trivial unavoided crossings, analysis of data based on transition densities, and efficient computational implementations of these numerical methods. We also emphasize newly developed semiclassical approaches, based on the Gaussian approximation, which retain phase and width information to account for significant decoherence and interference effects while maintaining the high efficiency of surface-hopping approaches. The above developments have been employed to successfully describe photophysics in a variety of molecular materials. |
