Evaluation of range-separated hybrid density functionals for the prediction of vibrational frequencies, infrared intensities, and Raman activities.
We present an assessment of different density functionals, with emphasis on range-separated hybrids, for the prediction of fundamental and harmonic vibrational frequencies, infrared intensities, and Raman activities. Additionally, we discuss the basis set convergence of vibrational properties of H2O with long-range corrected hybrids. Our results show that B3LYP is the best functional for predicting vibrational frequencies (both fundamental and harmonic); the screened-PBE hybrid (HSE) density functional works best for infrared intensities, and the long-range corrected PBE (LC-omegaPBE), M06-HF, and M06-L density functionals are almost as good as MP2 for predicting Raman activities. We show the predicted Raman spectrum of adenine as an example of a medium-size molecule where a DFT/Sadlej pVTZ calculation is affordable and compare our results against the experimental spectrum.
Jiménez-Hoyos
Carlos A
CA
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
Janesko
Benjamin G
BG
Scuseria
Gustavo E
GE
D000225:Adenine / Q000737:chemistry; D003198:Computer Simulation; D008958:Models, Molecular; D013055:Spectrophotometry, Infrared / Q000379:methods*; D013059:Spectrum Analysis, Raman / Q000379:methods*; D014732:Vibration; D014867:Water / Q000737:chemistry
D014867:Water; D000225:Adenine