Diabatic-At-Construction Method for Diabatic and Adiabatic Ground and Excited States Based on Multistate Density Functional Theory.
Diabatic-At-Construction Method for Diabatic and Adiabatic Ground and Excited States Based on Multistate Density Functional Theory.
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基于多态密度泛函理论的非绝热基态和激发态非绝热构造方法
DOI：
10.1021/acs.jctc.6b01176
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发表时间：
2017-03-14
影响因子：
5.5
通讯作者：
Gao J
中科院分区：
文献类型：
--
作者：
Grofe A;Qu Z;Truhlar DG;Li H;Gao J
本文利用多态密度泛函理论（MSDFT）描述了一种定义绝热态的非绝热构造（DAC）策略，以确定绝热基态和激发态及其势能面。DAC方法在两个基本方面不同于绝热到绝热（ATD）过程，将一组预先选择的绝热电子状态转换为新的表示。(1)在第一步计算中定义DAC状态形成一个主动空间，其组态相互作用在第二步产生绝热基态和激发态。因此，它们不是由ATD过程中绝热状态的相似变换产生的；它们是产生绝热态的基础。通过与基态和激发态实验观测值的比较，验证了DAC有源空间的适当性和完备性。(2) DAC非绝热态是根据所研究的绝热态的渐近解离极限的价键特征来定义的，它们在所有分子几何结构中都是严格保持的。因此，DAC绝热态具有明确的物理和化学意义，可用于理解绝热态的性质及其能量成分。在这里，我们给出了LiH的四个最低单重态的结果，并将它们与经过验证的ATD绝热方法（即3重法）进行了比较；通过比较，揭示了ATD非绝热状态与正交DAC非绝热状态的异同。此外，MSDFT可以提供LiH的基态和激发态的定量描述，其中包含跨越10 Å以上原子间分离的多个强和弱避免曲线交叉点。
We describe a diabatic-at-construction (DAC) strategy for defining diabatic states to determine the adiabatic ground and excited electronic states and their potential energy surfaces using the multistate density functional theory (MSDFT). The DAC approach differs in two fundamental ways from the adiabatic-to-diabatic (ATD) procedures that transform a set of preselected adiabatic electronic states to a new representation. (1) The DAC states are defined in the first computation step to form an active space, whose configuration interaction produces the adiabatic ground and excited states in the second step of MSDFT. Thus, they do not result from a similarity transformation of the adiabatic states as in the ATD procedure; they are the basis for producing the adiabatic states. The appropriateness and completeness of the DAC active space can be validated by comparison with experimental observables of the ground and excited states. (2) The DAC diabatic states are defined using the valence bond characters of the asymptotic dissociation limits of the adiabatic states of interest, and they are strictly maintained at all molecular geometries. Consequently, DAC diabatic states have specific and well-defined physical and chemical meanings that can be used for understanding the nature of the adiabatic states and their energetic components. Here we present results for the four lowest singlet states of LiH and compare them to a well-tested ATD diabatization method, namely the 3-fold way; the comparison reveals both similarities and differences between the ATD diabatic states and the orthogonalized DAC diabatic states. Furthermore, MSDFT can provide a quantitative description of the ground and excited states for LiH with multiple strongly and weakly avoided curve crossings spanning over 10 Å of interatomic separation.
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影响因子：
5.5
作者：
Cembran, Alessandro;Payaka, Apirak;Lin, Yen-lin;Xie, Wangshen;Mo, Yirong;Song, Lingchun;Gao, Jiali
通讯作者：
Gao, Jiali
影响因子：
4.4
作者：
HALVICK, P;TRUHLAR, DG
通讯作者：
TRUHLAR, DG
影响因子：
1.7
作者：
Habli, Hela;Mejrissi, Leila;Gadea, Florent Xavier
通讯作者：
Gadea, Florent Xavier
影响因子：
2.8
作者：
Bande, Annika;Nakashima, Hiroyuki;Nakatsuji, Hiroshi
通讯作者：
Nakatsuji, Hiroshi
影响因子：
4.4
作者：
Godsi, Oded;Evenhuis, Christian R.;Collins, Michael A.
通讯作者：
Collins, Michael A.