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

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