CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx)

摘要

In a recent work [Baudin and Kristensen, J. Chem. Phys. 144, 224106 (2016)],we introduced a local framework for calculating excitation energies (LoFEx),based on second-order approximated coupled cluster (CC2) linear-responsetheory. LoFEx is a black-box method in which a reduced excitation orbital space(XOS) is optimized to provide coupled cluster (CC) excitation energies at areduced computational cost. In this article, we present an extension of theLoFEx algorithm to the calculation of CC2 oscillator strengths. Two differentstrategies are suggested, in which the size of the XOS is determined based onthe excitation energy or the oscillator strength of the targeted transitions.The two strategies are applied to a set of medium-sized organic molecules inorder to assess both the accuracy and the computational cost of the methods.The results show that CC2 excitation energies and oscillator strengths can becalculated at a reduced computational cost, provided that the targetedtransitions are local compared to the size of the molecule. To illustrate thepotential of LoFEx for large molecules, both strategies have been successfullyapplied to the lowest transition of the bivalirudin molecule (4255 basisfunctions) and compared with time-dependent density functional theory.