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Configuration space partitioning and matrix buildup scaling for the vibrational configuration interaction method

Authors

  • Andriy Samsonyuk,

    1. Lehrstuhl für Theoretische Chemie, Technische Universität München, Lichtenbergstraβe 4, 85748 Garching, Germany
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  • Christoph Scheurer

    Corresponding author
    1. Lehrstuhl für Theoretische Chemie, Technische Universität München, Lichtenbergstraβe 4, 85748 Garching, Germany
    • Lehrstuhl für Theoretische Chemie, Technische Universität München, Lichtenbergstraβe 4, 85748 Garching, Germany
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Abstract

The accurate computation of anharmonic vibrational states for medium to large molecules is a requirement for the detailed understanding of nonlinear multidimensional infrared spectra and the dynamical information encoded in them. The vibrational configuration interaction (VCI) method constitutes a particularly promising tool in this respect. It is generally hampered though by its unfavorable scaling with respect to system size. We analyze the scaling behavior of several well-known as well as some new approximate VCI schemes in detail, which are complementary to the class of configuration selection schemes developed recently. We find that the combination of a configuration space partitioning, possibly based on configuration selection, with energetic thresholding and resonance screening provides an efficient scheme for the reduction of computational effort involved in VCI calculations while at the same time maintaining sufficient accuracy for the vibrational energies. © 2012 Wiley Periodicals, Inc.

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