期刊
JOURNAL OF CHEMICAL PHYSICS
卷 145, 期 20, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4967860
关键词
-
资金
- U.S. National Science Foundation [CHE-1566428]
We present the theory and implementation for calculating static polarizabilities within the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) framework for electronically excited states and its spin-flip variant. We evaluate the second derivatives of the EOM-CCSD Lagrangian with respect to electric-field perturbations. The relaxation of reference molecular orbitals is not included. In our approach, the wave function amplitudes satisfy the 2n + 1 rule and the amplitude-response Lagrange multipliers satisfy the 2n + 2 rule. The new implementation is validated against finite-field and CCSD response-theory calculations of the excited-state polarizabilities of pyrimidine and s-tetrazine. We use the new method to compute static polarizabilities of different types of electronic states (valence, charge-transfer, singlets, and triplets) in open-and closed-shell systems (uracil, p-nitroaniline, methylene, and p-benzyne). We also present an alternative approach for calculating excited-state static polarizabilities as expectation values by using the EOM-CCSD wave functions and energies in the polarizability expression for an exact state. We find that this computationally less demanding approach may show differences up to similar to 30% relative to the excited-state polarizabilities computed using the analytic-derivative formalism. Published by AIP Publishing.
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