A polarizable mixed Hamiltonian model of electronic structure for micro-solvated excited states. I. Energy and gradients formulation and application to formaldehyde (1A2)
A polarizable mixed Hamiltonian model of electronic structure for micro-solvated excited states. I. Energy and gradients formulation and application to formaldehyde (1A2)
复制标题
微溶剂化激发态电子结构的可极化混合哈密顿模型。
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;M. Aida;Y. Kawashima;K. Hirao
我们描述了一种将Hartree-Fock、Kohn-Sham或多组态量子化学波函数与水的可极化和灵活的分子力学势相结合的电子结构可极化混合哈密顿模型的有效实现，该模型适用于微溶剂电子激发态。我们采用直接算法来计算溶剂子系统的极化响应。该策略便于计算体系的能量和相对于溶质坐标和溶剂坐标的力，包括对激发态的能量。这一能力为确定溶质-溶剂系统的最优化过渡结构、力常数和本征反应路径以及考虑有限温度影响的分子动力学计算开辟了道路。作为例子，我们表征了微溶剂甲醛H_2CO在基态和其1(π*←_n)激发下的结构和能量。
We describe an efficient implementation of a polarizable mixed Hamiltonian model of electronic structure that combines Hartree–Fock, Kohn–Sham, or multiconfiguration quantum-chemical wave functions with a polarizable and flexible molecular mechanics potential of water, and that is applicable to micro-solvated electronic excited states. We adopt a direct algorithm for the calculation of the polarization response of the solvent subsystem. The strategy facilitates the calculation of the energy of the system and of the forces with respect to the solute coordinates and the solvent coordinates, including for excited states. This capability opens the way to the determination of optimized, transition structures, force constants, and intrinsic reaction pathways for the solute–solvent system, and to molecular dynamics calculations to account for finite temperature effects. As an illustration we characterize the structure and energy of micro-solvated formaldehyde H2CO in its ground state and in its 1(π*←n) excited s...