A polarizable mixed Hamiltonian model of electronic structure for solvated excited states. II. Application to the blue shift of the H2CO 1(π*←n) excitation in water
A polarizable mixed Hamiltonian model of electronic structure for solvated excited states. II. Application to the blue shift of the H2CO 1(π*←n) excitation in water
复制标题
溶剂化激发态的可极化混合哈密顿模型在水中 H2CO 1(π*←n) 激发的蓝移中的应用。
DOI：
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发表时间：
2002
期刊：
影响因子：
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通讯作者：
K. Hirao
中科院分区：
文献类型：
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作者：
M. Dupuis;Y. Kawashima;K. Hirao
我们举例说明了在同伴论文I中发展的极化混合哈密顿模型的应用[J]。化学。并描述了水中电子激发甲醛的结构。物理学报，117,1242(2002)]。我们使用Hartree-Fock和多组态波函数，结合tip3p、pol1和pol2相互作用势和Bartlett-Shavitt振动势对水进行分析。我们计算了H2CO （1A1, 3A2和1A2）与1个或2个水分子微溶剂化的结构，并模拟了多达81个具有平衡溶质-溶剂构型的水环境。我们计算了垂直激发能和绝热激发能。由于溶剂化，垂直吸收能量在~ 1000和~ 2500 cm−1之间显示出蓝移，这实际上已经存在于微溶剂化体系中，并且随着溶剂化程度的增加而增加。基态和激发态的偶极矩随溶剂化程度的增加而显著增加。极化特性…
We illustrate an application of a polarizable mixed Hamiltonian model of solvation developed in the companion Paper I [J. Chem. Phys. 117, 1242 (2002)] and describe the structure of electronically excited formaldehyde in water. We used Hartree-Fock and multiconfiguration wave functions together with the tip3p, pol1, and pol2 interaction potentials combined with the Bartlett–Shavitt vibrational potential for water. We calculated the structure of H2CO (1A1, 3A2, and 1A2) micro-solvated with 1 or 2 water molecules and we mimicked the aqueous environment with up to 81 waters with equilibrium solute–solvent configurations. We calculated the vertical and adiabatic excitations energies. The vertical absorption energy shows a blue shift between ∼1000 and ∼2500 cm−1 due to solvation, that is in fact already present in the micro-solvated systems and increases with the degree of solvation. The dipole moments of the ground and excited states show a marked increase with the degree of solvation. The polarizable charact...