Approaches for the calculation of vibrational frequencies in liquids: comparison to benchmarks for azide/water clusters.
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.
Li
Shuzhou
S
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Schmidt
J R
JR
Corcelli
S A
SA
Lawrence
C P
CP
Skinner
J L
JL
D001386:Azides / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods*; D004581:Electronics; D004583:Electrons; D007477:Ions; D008958:Models, Molecular; D008962:Models, Theoretical; D009991:Oscillometry; D013053:Spectrophotometry / Q000379:methods*; D055672:Static Electricity; D014732:Vibration; D014867:Water / Q000737:chemistry*
D001386:Azides; D007477:Ions; D014867:Water