Constructing diabatic representations using adiabatic and approximate diabatic data - Coping with diabolical singularities

被引:0
|
作者
Zhu, Xiaolei [1 ]
Yarkony, David R. [1 ]
机构
[1] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA
来源
JOURNAL OF CHEMICAL PHYSICS | 2016年 / 144卷 / 04期
基金
美国国家科学基金会;
关键词
POTENTIAL-ENERGY SURFACES; NONADIABATIC COUPLING TERMS; MR-CI LEVEL; CONICAL INTERSECTION; MOLECULAR-PROPERTIES; SUBSTITUTED PHENOLS; ANALYTIC EVALUATION; STATES; PHOTODISSOCIATION; COLLISIONS;
D O I
10.1063/1.4939765
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have recently introduced a diabatization scheme, which simultaneously fits and diabatizes adiabatic ab initio electronic wave functions, Zhu and Yarkony J. Chem. Phys. 140, 024112 (2014). The algorithm uses derivative couplings in the defining equations for the diabatic Hamiltonian, H-d, and fits all its matrix elements simultaneously to adiabatic state data. This procedure ultimately provides an accurate, quantifiably diabatic, representation of the adiabatic electronic structure data. However, optimizing the large number of nonlinear parameters in the basis functions and adjusting the number and kind of basis functions from which the fit is built, which provide the essential flexibility, has proved challenging. In this work, we introduce a procedure that combines adiabatic state and diabatic state data to efficiently optimize the nonlinear parameters and basis function expansion. Further, we consider using direct properties based diabatizations to initialize the fitting procedure. To address this issue, we introduce a systematic method for eliminating the debilitating (diabolical) singularities in the defining equations of properties based diabatizations. We exploit the observation that if approximate diabatic data are available, the commonly used approach of fitting each matrix element of H-d individually provides a starting point (seed) from which convergence of the full H-d construction algorithm is rapid. The optimization of nonlinear parameters and basis functions and the elimination of debilitating singularities are, respectively, illustrated using the 1,2,3,4(1)A states of phenol and the 1,2(1)A states of NH3, states which are coupled by conical intersections. (C) 2016 AIP Publishing LLC.
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页数:11
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