Basis set and density functional dependence of vibrational Raman optical activity calculations

Markus Reiher, V. Liégeois, K. Ruud

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We present an extensive investigation of the dependence of the scattering intensity difference of right and left circularly polarized light observed in vibrational Raman optical activity (VROA) on the choice of basis set and exchange-correlation functional. These dependencies are investigated for five molecules for which accurate experimental data are available: (S)-methyloxirane, (R)-epichlorhydrin, (S')-glycidol, (M)-spiro[2,2]-pentane-1,4-diene, and (M)-σ-[4]-helicene. Calculations are presented using the SVWN exchange-correlation functional (LDA), the BLYP exchange-correlation functional, and the B3LYP hybrid functional, using six different basis sets: the cc-pVDZ, cc-pVTZ, aug-cc-pVDZ, aug-cc-pVTZ, Sadlej's polarized basis set, and a minimal VROA basis set recently proposed by Zuber and Hug. It is demonstrated that results from pure gradient-corrected and hybrid functionals are comparable and that the aug-cc-pVDZ and aug-cc-pVTZ basis sets yield similar results. Furthermore, the combination of the small basis set by Zuber and Hug with an accurate force field represents the best compromise between computational accuracy and computational efficiency.
Original languageEnglish
Pages (from-to)7567-7574
Number of pages8
JournalJournal of physical chemistry A
Issue number33
Publication statusPublished - 25 Aug 2005


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