Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 15, Issue 9, Pages 4790-4803Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.9b00351
Keywords
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Funding
- Early Career Research Program of the Office of Science, Office of Basic Energy Sciences, U.S. Department of Energy [DE-SC0017869]
- National Science Foundation's Graduate Research Fellowship Program
- U.S. Department of Energy (DOE) [DE-SC0017869] Funding Source: U.S. Department of Energy (DOE)
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We present a method for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties due to root flipping and near-degeneracies. Inspired by both the maximum overlap method and recent progress in excited-state variational principles, our approach combines these ideas in order to track individual excited states throughout the orbital optimization process. In a series of tests involving root flipping, near-degeneracies, charge transfers, and double excitations, we show that this approach is more effective for state-specific optimization than either the naive selection of roots on the basis of energy ordering or a more direct generalization of the maximum overlap method. We provide evidence that this state-specific approach improves the performance of complete active space perturbation theory for vertical excitation energies. Furthermore, we find that the state-specific optimization can help avoid state-averaging-induced discontinuities on potential energy surfaces. With a simple implementation, a low cost, and compatibility with large active space methods, the approach is designed to be useful in a wide range of excited-state investigations.
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