Calculation of two-photon absorption strengths with the approximate coupled cluster singles and doubles model CC2 using the resolution-of-identity approximation

Daniel H. Friesea, Christof Hättiga, and Kenneth Ruudb
a Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44801 Bochum, Germany
b Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N+9037 Tromsø, Norway

Phys. Chem. Chem. Phys. 14, 1175-1184 (2012)
(Received 26th September 2011; accepted 4th November 2011)

An implementation of two-photon absorption matrix elements using the approximate second-order coupled-cluster singles and doubles model CC2 is presented. In this implementation we use the resolution-of-the-identity approximation for the two-electron repulsion integrals to reduce the computational cost. To avoid storage of large arrays we introduce in addition a numerical Laplace transformation of orbital energy denominators for the response of the doubles amplitudes. The error due to the numerical Laplace transformation is found to be negligible. Using this new implementation, we performed a series of benchmark calculations on substituted benzene and azobenzene derivatives to get reference values for TD-DFT results. We show that results obtained with the Coulomb-attenuated B3LYP functional are in reasonable agreement with the coupled-cluster results, whereas other density functionals which do not have a long-range correction give considerably less accurate results. Applications to the AF240 dye molecule and a weakly bound molecular tweezer complex demonstrate that this new RI-CC2 implementation allows for the first time to compute two-photon absorption cross sections with a correlated wave function method for molecules with more than 70 atoms and to apply this method for benchmarking TD-DFT calculations on molecules which are of particular relevance for experimental studies of two-photon absorption.

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