title: Theoretical studies of the tunneling splitting of malonaldehyde using the multiconfiguration time-dependent Hartree approach.
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.
authors.affiliation: Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany. markus.schroeder@pci.uni-heidelberg.de
authors.forename: Markus
authors.initials: M
authors.lastname: Schröder
authors.forename: Fabien
authors.initials: F
authors.lastname: Gatti
authors.forename: Hans-Dieter
authors.initials: HD
authors.lastname: Meyer
mesh_terms: D007700:Kinetics; D008315:Malondialdehyde / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013499:Surface Properties; D013997:Time Factors
chemical_list: D008315:Malondialdehyde