Xu ZongRong, Matsika Spiridoula
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA.
J Phys Chem A. 2006 Nov 2;110(43):12035-43. doi: 10.1021/jp064520d.
A combined quantum mechanics/molecular mechanics method is described here for considering the solvatochromic shift of excited states in solution. The quantum mechanical solute is described using high level multireference configuration interaction methods (MRCI), while molecular dynamics is used for obtaining the structure of the solvent around the solute. The electrostatic effect of the solvent is included in the quantum description of the solute in an averaged way. This method is used to study solvent effects on the n(O) --> pi* electronic transition of formaldehyde in aqueous solution. The effects of solute polarization, basis sets, and dynamical correlation on the solvatochromic shift, and on dipole moments, have been investigated.
本文描述了一种结合量子力学/分子力学的方法，用于考虑溶液中激发态的溶剂化显色位移。采用高水平多参考组态相互作用方法（MRCI）描述量子力学溶质，同时利用分子动力学获得溶质周围溶剂的结构。溶剂的静电效应以平均方式包含在溶质的量子描述中。该方法用于研究溶剂对水溶液中甲醛n(O)→π*电子跃迁的影响。研究了溶质极化、基组和动态相关性对溶剂化显色位移以及偶极矩的影响。
