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Excited State Orbital Optimization via Minimizing the Square of the Gradient: General Approach and Application to Singly and Doubly Excited States via Density Functional Theory

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Div.
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We present a general approach to converge excited state solutions to any quantum chemistry orbital optimization process, without the risk of variational collapse. The resulting square gradient minimization (SGM) approach only requires analytic energy/Lagrangian orbital gradients and merely costs 3 times as much as ground state orbital optimization (per iteration), when implemented via a finite difference approach. SGM is applied to both single determinant ΔSCF and spin-purified restricted open-shell Kohn-Sham (ROKS) approaches to study the accuracy of orbital optimized DFT excited states. It is found that SGM can converge challenging states where the maximum overlap method (MOM) or analogues either collapse to the ground state or fail to converge. We also report that ΔSCF/ROKS predict highly accurate excitation energies for doubly excited states (which are inaccessible via TDDFT). Singly excited states obtained via ROKS are also found to be quite accurate, especially for Rydberg states that frustrate (semi)local TDDFT. Our results suggest that orbital optimized excited state DFT methods can be used to push past the limitations of TDDFT to doubly excited, charge-transfer, or Rydberg states, making them a useful tool for the practical quantum chemist's toolbox for studying excited states in large systems.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1779239
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 3 Vol. 16; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Highly Accurate Prediction of Core Spectra of Molecules at Density Functional Theory Cost: Attaining Sub-electronvolt Error from a Restricted Open-Shell Kohn–Sham Approach journal January 2020
An Overview of Self-Consistent Field Calculations Within Finite Basis Sets journal March 2020
An overview of self-consistent field calculations within finite basis sets text January 2019

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