Theoretical studies of the tunneling splitting of malonaldehyde using the multiconfiguration time-dependent Hartree approach

• Verfasst von: Schröder, Markus [VerfasserIn]
• Verfasst von: Gatti, Fabien [VerfasserIn]
• Verfasst von: Meyer, Hans-Dieter [VerfasserIn]
• Titel: Theoretical studies of the tunneling splitting of malonaldehyde using the multiconfiguration time-dependent Hartree approach
• Verf.angabe: Markus Schröder, Fabien Gatti, and Hans-Dieter Meyer
• E-Jahr: 2011
• Jahr: 17 June 2011
• Umfang: 10 S.
• Illustrationen: Illustrationen
• Fussnoten: Gesehen am 26.10.2022
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2011
• Band/Heft Quelle: 134(2011), 23 vom: Juni, Artikel-ID 234307, Seite 1-10
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/1.3600343
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1820049809

Abstract

Full dimensional multi-configuration time-dependent Hartree calculations of the zero point energy and the tunneling splitting of malonaldehyde using a recently published potential energy surface [Y. Wang, B. J. Braams, J. M. Bowman, S. Carter, and D. P. Tew, J. Chem. Phys. 128, 224314 (2008)] are reported. The potential energy surface has been approximated by a modified version of the n-mode representation and careful convergence check has been performed to ensure accurate results. The obtained value for the splitting (23.4 cm−1) is in acceptable agreement with the experimental value of 21.583 cm−1. The computed zero-point-energy is 14 670 cm−1 which is lower than previous results of Wang et al., but likely to be about 4 cm−1 too low because of shortcomings of the n-mode representation of the potential. The energies reported in this abstract contain a correction to account for neglected vibrational angular momentum terms.