Two-photon absorption cross sections within equation-of-motion coupled-cluster formalism using resolution-of-the-identity and Cholesky decomposition representations: Theory, implementation, and benchmarks

K. Nanda and A.I. Krylov
J. Chem. Phys. 142, 064118 (2015)

The equation-of-motion coupled-cluster (EOM-CC) methods provide a robust description of electronically excited states and their properties. Here we present a formalism for two-photon absorption (2PA) cross sections for the EOM-EE-CCSD (EOM-CC for electronically excited states with single and double substitutions) wave functions. Instead of the response theory formulation, we employ the expectation-value approach which is commonly used within EOM-CC, configuration interaction, and algebraic diagramatic construction frameworks. In addition to canonical implementation, we also exploit resolution-of-the-identity (RI) and Cholesky decomposition (CD) for the electron-repulsion integrals to reduce memory requirements and to increase parallel efficiency. The new methods are benchmarked against the CCSD and CC3 response theory for several small molecules. We found that the expectation-value 2PA cross sections are within 1-3 % from the quadratic response CCSD values. The RI and CD approximations lead to small errors relative to the canonical implementation (less than 4 %) while affording computational savings. RI/CD successfully address the well-known issue of large basis set requirements for 2PA cross sections calculations. The capabilities of the new code are illustrated by calculations of the 2PA cross sections for model chromophores of the photoactive yellow and green fluorescent proteins.

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