Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 13, Issue 6, Pages 2561-2570Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.7b00018
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Funding
- Air Force Office of Scientific Research [FA9550-15-1-0031]
- National Science Foundation [ACI-1550481, CHE-1351598]
- Direct For Computer & Info Scie & Enginr
- Office of Advanced Cyberinfrastructure (OAC) [1550481] Funding Source: National Science Foundation
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1351598] Funding Source: National Science Foundation
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The probability of nonradiative transitions in photochemical dynamics is determined by the derivative couplings, the couplings between different electronic states through the nuclear degrees of freedom. Efficient and accurate evaluation of the derivative couplings is, therefore, of central importance to realize reliable computer simulations of photochemical reactions. In this work, the derivative couplings for multistate multireference second-order perturbation theory (MS-CASPT2) and its extended variant (XMS-CASPT2) are studied, in which we present an algorithm for their analytical evaluation. The computational costs for evaluating the derivative couplings are essentially the same as those for calculating the nuclear energy gradients. The geometries and energies calculated with XMS-CASPT2 for small molecules at minimum energy conical intersections (MECIs) are in good agreement with those computed by multireference configuration interaction. As numerical examples, MECIs are optimized using XMS-CASPT2 for stilbene and a green fluorescent protein model chromophore (the 4-para-hydroxybenzylidene-1,2-dimethyl-imidazolin-5-one anion).
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