Issue 47, 2015

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

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

Article information

Article type
Paper
Submitted
19 Jan 2015
Accepted
08 Apr 2015
First published
27 Apr 2015
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2015,17, 31453-31462

Author version available

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

J. S. Kottmann, S. Höfener and F. A. Bischoff, Phys. Chem. Chem. Phys., 2015, 17, 31453 DOI: 10.1039/C5CP00345H

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