title: A DFT conformational analysis and VCD study on methyl tetrahydrofuran-2-carboxylate.
abstract: DFT calculations were performed on (S)-methyl tetrahydrofuran-2-carboxylate to facilitate the interpretation of IR and VCD spectra. The potential energy surface could not be described unambiguously using the 6-31G* basis set in combination with different density functionals including B1LYP, B3LYP, B3P86, B3PW91, B98, BHandH, BHandHLYP, MPW1PW91 and PBE1PBE. In contrast, a uniform conformational picture could be found using the cc-pVTZ basis set. Using this large basis set and the collection of nine functionals from above, the dipole and rotational strengths were calculated, and compared to experimental values which were extracted from the experimental IR and VCD spectra for (+)-(S)-methyl tetrahydrofuran-2-carboxylate. A detailed analysis on the agreement between experiment and simulated spectra was performed by assigning the experimental bands based on the harmonic fundamentals obtained for all functionals except BHandH, which performs badly over the whole line. Assessing the dipole strengths, all tested functionals perform equally well. For the rotational strengths, differences can be observed: B3LYP, B1LYP and B98 give the highest correlation with experiment, while PBE1PBE gives the lowest correlation. Comparable conclusions are obtained using a neighborhood similarity measure.
authors.affiliation: Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281, S3, B-9000 Ghent, Belgium.
authors.forename: Tom
authors.initials: T
authors.lastname: Kuppens
authors.forename: Koen
authors.initials: K
authors.lastname: Vandyck
authors.forename: Johan
authors.initials: J
authors.lastname: van der Eycken
authors.forename: Wouter
authors.initials: W
authors.lastname: Herrebout
authors.forename: Benjamin
authors.initials: B
authors.lastname: van der Veken
authors.forename: Patrick
authors.initials: P
authors.lastname: Bultinck
mesh_terms: D002942:Circular Dichroism; D004952:Esters / Q000737:chemistry*; D005663:Furans / Q000737:chemistry*; D008432:Mathematical Computing; D008968:Molecular Conformation; D013055:Spectrophotometry, Infrared
chemical_list: D004952:Esters; D005663:Furans; C522619:methyl tetrahydrofuran-2-carboxylate