Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 142, Issue 6, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4907376
Keywords
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Funding
- National Science Foundation [CHE-1300603]
- Ohio Supercomputer Center [PAA-0003]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1300603] Funding Source: National Science Foundation
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We revisit the formalism for analytic derivative couplings between excited states in time-dependent density functional theory (TDDFT). We derive and implement these couplings using quadratic response theory, then numerically compare this response-theory formulation to couplings implemented previously based on a pseudo-wavefunction formalism and direct differentiation of the Kohn-Sham determinant. Numerical results, including comparison to full configuration interaction calculations, suggest that the two approaches perform equally well for many molecular systems, provided that the underlying DFT method affords accurate potential energy surfaces. The response contributions are found to be important for certain systems with high symmetry, but can be calculated with only a moderate increase in computational cost beyond what is required for the pseudo-wavefunction approach. In the case of spin-flip TDDFT, we provide a formal proof that the derivative couplings obtained using response theory are identical to those obtained from the pseudo-wavefunction formulation, which validates our previous implementation based on the latter formalism. (C) 2015 AIP Publishing LLC.
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