Nonadiabatic Excited-State Dynamics with Hybrid ab Initio Quantum-Mechanical/Molecular-Mechanical Methods: Solvation of the Pentadieniminium Cation in Apolar Media

Autor:	Mario Barbatti, Hans Lischka, Thomas Müller, Matthias Ruckenbauer
Rok vydání:	2010
Předmět:	Models Molecular Time Factors Chemistry Molecular Conformation Ab initio Solvation Chromophore Chemical physics Cations Excited state Solvents Quantum Theory Molecule Imines Physical and Theoretical Chemistry Atomic physics Quantum
Zdroj:	The Journal of Physical Chemistry A. 114:6757-6765
ISSN:	1520-5215 1089-5639
Popis:	A new implementation of nonadiabatic excited-state dynamics using hybrid methods is presented. The current approach is aimed at the simulation of photoexcited molecules in solution. The chromophore is treated at the ab initio level, and its interaction with the solvent is approximated by point charges within the electrostatic embedding approach and by a Lennard-Jones potential for the nonbonded interactions. Multireference configuration interaction (MRCI) and multiconfiguration self-consistent field (MCSCF) methods can be used. The program implementation has been performed on the basis of the Columbus and Newton-X program systems. For example, the dynamics of penta-2,4-dien-1-iminium (PSB3) and 4-methyl-penta-2,4-dien-1-iminium cations (MePSB3) was investigated in gas phase and in n-hexane solution. The excited-state (S(1)) lifetime and temporal evolution of geometrical parameters were computed. In the case of PSB3 the n-hexane results resemble closely the gas phase data. MePSB3, however, shows a distinct extension of lifetime due to steric hindering of the torsion around the central bond because of solute-solvent interactions.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::ebb4b0db8167cff381ff21e8d5979db7 https://doi.org/10.1021/jp103101t Zobrazit plný text záznamu