Abstract
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 language | English |
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Pages (from-to) | 7567-7574 |
Number of pages | 8 |
Journal | Journal of physical chemistry A |
Volume | 109 |
Issue number | 33 |
DOIs | |
Publication status | Published - 25 Aug 2005 |
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Dive into the research topics of 'Basis set and density functional dependence of vibrational Raman optical activity calculations'. Together they form a unique fingerprint.Student theses
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Elaboration of quantum chemistry methods for predicting and interpreting vibrational Raman optical activity: applications to helical structures
Author: Liégeois, V., 19 Jun 2008Supervisor: Thiry, P. (Jury), Verbiest, T. (External person) (Jury), Hug, W. (External person) (Jury), Ruud, K. (External person) (Jury), Su, B. L. (Jury) & Champagne, B. (Supervisor)
Student thesis: Doc types › Doctor of Sciences