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Issue 47, 2015
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Numerically accurate linear response-properties in the configuration-interaction singles (CIS) approximation

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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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Publication details

The article was received on 19 Jan 2015, accepted on 08 Apr 2015 and first published on 27 Apr 2015


Article type: Paper
DOI: 10.1039/C5CP00345H
Citation: Phys. Chem. Chem. Phys., 2015,17, 31453-31462
  • Open access: Creative Commons BY license
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    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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