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Diabatic-At-Construction Method for Diabatic and Adiabatic Ground and Excited States Based on Multistate Density Functional Theory

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3];  [2];  [4]
  1. Jilin Univ., Changchun (China). Inst. of Theoretical Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Supercomputing Inst.; OSTI
  2. Jilin Univ., Changchun (China). Inst. of Theoretical Chemistry
  3. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Supercomputing Inst.
  4. Jilin Univ., Changchun (China). Inst. of Theoretical Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry and Supercomputing Inst.
+ Show Author Affiliations
Here, 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.
Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
National Inst. of Health (NIH); National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0015997; SC0016214
OSTI ID:
1462349
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 3 Vol. 13; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Combined Multistate and Kohn-Sham Density Functional Theory Studies of the Elusive Mechanism of N-Dealkylation of N,N-Dimethylanilines Mediated by the Biomimetic Nonheme Oxidant FeIV(O)(N4Py)(ClO4)2 journal September 2018
Diabatic Hamiltonian Construction in van der Waals heterostructure complexes preprint January 2019

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