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

TL;DR

This paper extends the LoFEx method to compute CC2 oscillator strengths efficiently by optimizing excitation orbital spaces, enabling accurate calculations for large molecules at reduced computational costs.

Contribution

The paper introduces two strategies for calculating CC2 oscillator strengths within the LoFEx framework, enhancing efficiency for large molecular systems.

Findings

CC2 excitation energies and oscillator strengths can be computed efficiently.

The methods are accurate when targeted transitions are local.

Successful application to large molecules like bivalirudin.

Abstract

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-response theory. LoFEx is a black-box method in which a reduced excitation orbital space (XOS) is optimized to provide coupled cluster (CC) excitation energies at a reduced computational cost. In this article, we present an extension of the LoFEx algorithm to the calculation of CC2 oscillator strengths. Two different strategies are suggested, in which the size of the XOS is determined based on the excitation energy or the oscillator strength of the targeted transitions. The two strategies are applied to a set of medium-sized organic molecules in order to assess both the accuracy and the computational cost of the methods. The results show that CC2 excitation energies and oscillator strengths can be calculated at a reduced computational cost, provided that the targeted transitions are local compared to the size of the molecule. To illustrate the potential of LoFEx for large molecules, both strategies have been successfully applied to the lowest transition of the bivalirudin molecule (4255 basis functions) and compared with time-dependent density functional theory.