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首页> 外文期刊>The Journal of Chemical Physics >MULTICONFIGURATIONAL SELF-CONSISTENT REACTION FIELD THEORY FOR NONEQUILIBRIUM SOLVATION
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MULTICONFIGURATIONAL SELF-CONSISTENT REACTION FIELD THEORY FOR NONEQUILIBRIUM SOLVATION

机译：非平衡固溶的多构型自洽反应场理论

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We present multiconfigurational self-consistent reaction field theory and implementation for solvent effects on a solute molecular system that is not in equilibrium with the outer solvent. The approach incorporates two different polarization vectors for studying the influence of the solvent. The solute, an atom, a molecule or a supermolecule, is assumed to be surrounded by a linear, homogeneous medium described by two polarization vector fields, the optical polarization vector and the inertial polarization vector fields. The optical polarization vector is always in equilibrium with the actual electronic structure whereas the inertial polarization vector is not necessarily in equilibrium with the actual electronic structure. The electronic structure of the compound is described by a correlated electronic wave function-a multiconfigurational self-consistent field (MCSCF) wave function. This wave function is fully optimized with respect to all variational parameters in the presence of the surrounding polarizable dielectric medium having two distinct polarization vectors. We develop from a compact and simple expression a direct and second-order convergent optimization procedure for the solvent states influenced by the two types of polarization vectors. The general treatment of the correlation problem through the use of complete and restricted active space methodologies makes the present multiconfigurational self-consistent reaction field approach general in that it can handle any type of state, open-shell, excited, and transition states. We demonstrate the theory by computing solvatochromatic shifts in optical/UV spectra of some small molecules and electron ionization and electron detachment energies of the benzene molecule. It is shown that the dependency of the solvent induced affinity in benzene is nonmonotonic with respect the optical dielectric constant if inertial polarization effects also are accounted for. (C) 1995 American Institute of Physics. [References: 68]
机译：我们提出了多构型自洽反应场理论和实现对与外部溶剂不平衡的溶质分子系统的溶剂影响。该方法结合了两种不同的极化矢量，用于研究溶剂的影响。假定溶质，原子，分子或超分子被线性均质介质包围，该介质由两个偏振矢量场，光学偏振矢量场和惯性偏振矢量场描述。光学偏振矢量始终与实际电子结构保持平衡，而惯性偏振矢量不一定与实际电子结构保持平衡。化合物的电子结构由相关的电子波函数-多结构自洽场（MCSCF）波函数描述。在具有两个不同极化矢量的周围可极化介电介质的存在下，针对所有变化参数对该波函数进行了充分优化。我们从紧凑和简单的表达式开发了一种针对两种极化矢量影响的溶剂状态的直接和二阶收敛优化程序。通过使用完整和受限的活动空间方法对相关问题进行的一般处理，使得本发明的多构型自洽反应场方法变得通用，因为它可以处理任何类型的状态，开壳状态，激发状态和过渡状态。我们通过计算一些小分子的光学/紫外光谱中的溶剂化色移以及苯分子的电子电离和电子离解能来论证该理论。已经表明，如果还考虑惯性偏振效应，则溶剂诱导的苯亲和力的依赖性相对于光学介电常数是非单调的。 （C）1995年美国物理研究所。 [参考：68]

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