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Propagative block diagonalization diabatization of DFT/MRCI electronic states
The Journal of Chemical Physics ( IF 4.4 ) Pub Date : 2020-03-18 , DOI: 10.1063/1.5143126
Simon P. Neville 1 , Issaka Seidu 1 , Michael S. Schuurman 1, 2
Affiliation  

We present a framework for the calculation of diabatic states using the combined density functional theory and multireference configuration interaction (DFT/MRCI) method. Due to restrictions present in the current formulation of the DFT/MRCI method (a lack of analytical derivative couplings and the inability to use non-canonical Kohn–Sham orbitals), most common diabatization strategies are not applicable. We demonstrate, however, that diabatic wavefunctions and potentials can be reliably calculated at the DFT/MRCI level of theory using a propagative variant of the block diagonalization diabatization method (P-BDD). The proposed procedure is validated via the calculation of diabatic potentials for LiH and the simulation of the vibronic spectrum of pyrazine. In both cases, the combination of the DFT/MRCI and P-BDD methods is found to correctly recover the non-adiabatic coupling effects of the problem.

中文翻译:

DFT / MRCI电子态的传播块对角化绝热

我们提出了使用组合密度泛函理论和多参考配置相互作用(DFT / MRCI)方法计算非绝热态的框架。由于DFT / MRCI方法的当前公式存在局限性(缺乏分析性导数耦合,并且无法使用非规范的Kohn-Sham轨道),因此最不适用的绝热策略不适用。但是,我们证明,使用块对角化绝热方法(P-BDD)的传播变体,可以在DFT / MRCI理论水平上可靠地计算出绝热波函数和电势。通过计算LiH的非绝热势和模拟吡嗪的振动光谱,验证了所提出的方法。在这两种情况下
更新日期:2020-03-21
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