Approaches for the calculation of vibrational frequencies in liquids: comparison to benchmarks for azide/water clusters

J Chem Phys. 2006 May 28;124(20):204110. doi: 10.1063/1.2200690.

Abstract

Ultrafast vibrational spectroscopy experiments, together with molecular-level theoretical interpretation, can provide important information about the structure and dynamics of complex condensed phase systems, including liquids. The theoretical challenge is to calculate the instantaneous vibrational frequencies of a molecule in contact with a molecular environment, accurately and quickly, and to this end a number of different methods have been developed. In this paper we critically analyze these different methods by comparing their results to accurate benchmark calculations on azide/water clusters. We also propose an optimized quantum mechanics/molecular mechanics method, which for this problem is superior to the other methods.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Azides / chemistry*
  • Chemistry, Physical / methods*
  • Electronics
  • Electrons
  • Ions
  • Models, Molecular
  • Models, Theoretical
  • Oscillometry
  • Spectrophotometry / methods*
  • Static Electricity
  • Vibration
  • Water / chemistry*

Substances

  • Azides
  • Ions
  • Water