title: Intramolecular proton transfer in malonaldehyde: accurate multilayer multi-configurational time-dependent Hartree calculations.
abstract: Full-dimensional (multilayer) multi-configurational time-dependent Hartree calculations studying the intramolecular proton transfer in malonaldehyde based on a recent potential energy surface (PES) [Wang et al., J. Chem. Phys. 128, 224314 (2008)] are presented. The most accurate calculations yield a ground state tunneling splitting of 23.8 cm(-1) and a zero point energy of 14,678 cm(-1). Extensive convergence tests indicate an error margin of the quantum dynamics calculations for the tunneling splitting of about 0.2 cm(-1). These results are to be compared with the experimental value of the tunneling splitting of 21.58 cm(-1) and results of Monte Carlo calculations of Wang et al. on the same PES which yielded a zero point energy of 14,677.9 cm(-1) with statistical errors of 2-3 cm(-1) and a tunneling splitting of 21.6 cm(-1). The present data includes contributions resulting from the vibrational angular momenta to the tunneling splitting and the zero point energy of 0.2 cm(-1) and 2.4 cm(-1), respectively, which have been computed using a perturbative approach.
authors.affiliation: Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld, Germany. thorsten.hammer@uni-bielefeld.de
authors.forename: Thorsten
authors.initials: T
authors.lastname: Hammer
authors.forename: Uwe
authors.initials: U
authors.lastname: Manthe
mesh_terms: D008315:Malondialdehyde / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory; D013499:Surface Properties; D013997:Time Factors
chemical_list: D011522:Protons; D008315:Malondialdehyde