title: Largely reduced grid densities in a vibrational self-consistent field treatment do not significantly impact the resultingwavenumbers.
abstract: Especially for larger molecules relevant to life sciences, vibrational self-consistent field (VSCF) calculations can become unmanageably demanding even when only first and second order potential coupling terms are considered. This paper investigates to what extent the grid density of the VSCF's underlying potential energy surface can be reduced without sacrificing accuracy of the resulting wavenumbers. Including single-mode and pair contributions, a reduction to eight points per mode did not introduce a significant deviation but improved the computational efficiency by a factor of four. A mean unsigned deviation of 1.3% from the experiment could be maintained for the fifteen molecules under investigation and the approach was found to be applicable to rigid, semi-rigid and soft vibrational problems likewise. Deprotonated phosphoserine, stabilized by two intramolecular hydrogen bonds, was investigated as an exemplary application.
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, Innsbruck 6020, Austria. oliver.lutz@uibk.ac.at.
authors.forename: Oliver M D
authors.initials: OM
authors.lastname: Lutz
authors.affiliation: Institute of General, Inorganic and Theoretical Chemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, Innsbruck 6020, Austria. bernd.m.rode@uibk.ac.at.
authors.forename: Bernd M
authors.initials: BM
authors.lastname: Rode
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, Innsbruck 6020, Austria. guenther.bonn@uibk.ac.at.
authors.forename: Günther K
authors.initials: GK
authors.lastname: Bonn
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, Innsbruck 6020, Austria. christian.w.huck@uibk.ac.at.
authors.forename: Christian W
authors.initials: CW
authors.lastname: Huck
mesh_terms: D000465:Algorithms; D006860:Hydrogen Bonding; D008956:Models, Chemical; D010768:Phosphoserine / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D010768:Phosphoserine