TY - JOUR
T1 - Nonadiabatic excited-state dynamics with hybrid ab initio quantum-mechanical/molecular-mechanical methods
T2 - Solvation of the pentadieniminium cation in apolar media
AU - Ruckenbauer, Matthias
AU - Barbatti, Mario
AU - Müller, Thomas
AU - Lischka, Hans
PY - 2010/7/1
Y1 - 2010/7/1
N2 - 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 (S1) 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.
AB - 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 (S1) 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.
UR - http://www.scopus.com/inward/record.url?scp=77954018078&partnerID=8YFLogxK
U2 - 10.1021/jp103101t
DO - 10.1021/jp103101t
M3 - Article
C2 - 20518515
AN - SCOPUS:77954018078
SN - 1089-5639
VL - 114
SP - 6757
EP - 6765
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 25
ER -