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Numerically accurate linear response-properties in the configuration-interaction singles (CIS) approximation
Jakob S. Kottmann,Sebastian Höfener,Florian A. Bischoff
Physical Chemistry Chemical Physics Pub Date : 04/27/2015 00:00:00 , DOI:10.1039/C5CP00345H
Abstract

In the present work, we report an efficient implementation of configuration interaction singles (CIS) excitation energies and oscillator strengths using the multi-resolution analysis (MRA) framework to address the basis-set convergence of excited state computations. In MRA (ground-state) orbitals, excited states are constructed adaptively guaranteeing an overall precision. Thus not only valence but also, in particular, low-lying Rydberg states can be computed with consistent quality at the basis set limit a priori, or without special treatments, which is demonstrated using a small test set of organic molecules, basis sets, and states. We find that the new implementation of MRA-CIS excitation energy calculations is competitive with conventional LCAO calculations when the basis-set limit of medium-sized molecules is sought, which requires large, diffuse basis sets. This becomes particularly important if accurate calculations of molecular electronic absorption spectra with respect to basis-set incompleteness are required, in which both valence as well as Rydberg excitations can contribute to the molecule's UV/VIS fingerprint.

Graphical abstract: Numerically accurate linear response-properties in the configuration-interaction singles (CIS) approximation
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