Configuration space partitioning and matrix buildup scaling for the vibrational configuration interaction method. Issue 1 (31st August 2012)

• Record Type: Journal Article
• Authors: Samsonyuk, Andriy; Scheurer, Christoph
• Is Part Of: Journal of computational chemistry. Volume 34:Issue 1(2013)
• Page Start: 27
• Page End: 37
• Publication Date: 2012-08-31
• Subjects: Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23101
• Languages: English
• ISSNs: 0192-8651

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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.</p> </abstract>