Diabatic States at Construction (DAC) through Generalized Singular Value Decomposition.
Diabatic States at Construction (DAC) through Generalized Singular Value Decomposition.
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DOI：
10.1021/acs.jpclett.8b02472
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发表时间：
2018-10
期刊：
影响因子：
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通讯作者：
Meiyi Liu;Xin Chen;Adam Grofe;Jiali Gao
中科院分区：
文献类型：
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作者：
Meiyi Liu;Xin Chen;Adam Grofe;Jiali Gao
提出了一种通过广义奇异值分解将绝热势能面转化为非绝热表象的方法，称为广义非绝热构造法。首先，我们使用一组定域的、类似价键的配置态函数，称为DAC，作为基态。然后，用多态密度泛函理论(MSDFT)确定了绝热基态和相应的激发态。GDAC不同于传统的基于绝热到非绝热变换的方法，它具有一定的性质约束。以溶剂分子极化的CH3OCH2Cl一级键解离反应、氨二聚体光解的基态和一级激发态势能面附近的基态和一级激发态势能面以及氢化锂解离过程中的多次避免曲线交叉为例，说明了该方法的应用。在蛋白质的电子转移和质子耦合电子转移反应的研究中，GDAC脱氢方法可用于确定电荷定域态。
A procedure, called generalized diabatic-at-construction (GDAC), is presented to transform adiabatic potential energy surfaces into a diabatic representation by generalized singular value decomposition. First, we use a set of localized, valence bond-like configuration state functions, called DAC, as the basis states. Then, the adiabatic ground and relevant excited states are determined using multistate density functional theory (MSDFT). GDAC differs in the opposite direction from traditional approaches based on adiabatic-to-diabatic transformation with certain property restraints. The method is illustrated with applications to a model first-order bond dissociation reaction of CH3OCH2Cl polarized by a solvent molecule, the ground- and first-excited-state potential energy surfaces near the minimum conical intersection for the ammonia dimer photodissociation, and the multiple avoided curve crossings in the dissociation of lithium hydride. The GDAC diabatization method may be useful for defining charge-localized states in studies of electron transfer and proton-coupled electron transfer reactions in proteins.