Origin-independent two-photon circular dichroism calculations in coupled cluster theory

Daniel H. Friesea, Christof Hättiga, and Antonio Rizzob
b Centre for Theoretical and Computational Chemistry, University of Tromsø Tromø, Norway b Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44801 Bochum, Germany c Consiglio Nazionale delle Ricerche - CNR, Istituto per i Processi Chimico-Fisici, Pisa, Italy

Phys. Chem. Chem. Phys., 18, 13683-13692 (2016)
(Received 10th March 2016; accepted 7th April 2016)

We present the first origin-independent approach for the treatment of two-photon circular dichroism (TPCD) using coupled cluster methods. The approach is assessed concerning its behavior on the choice of the basis set and different coupled cluster methods. We also provide a comparison of results from CC2 with those from density functional theory using the CAM-B3LYP functional. Concerning the basis set we note that in most cases an augmented triple zeta basis or a doubly augmented double zeta basis is needed for reasonably converged results. In the comparison of different coupled cluster methods results from CCSD, CC3 and CC2 have been found to be quite similar in most cases, while CCS results differ remarkably from the results at the higher levels. However, this proof-of-principle study also shows that further benchmarking of DFT and CC2 against accurate coupled cluster reference values (e.g. CCSD or CC3) is needed.

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