Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
J Chem Phys. 2011 Jun 21;134(23):234307. doi: 10.1063/1.3600343.
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.
采用最近发表的势能面[Y. Wang、B. J. Braams、J. M. Bowman、S. Carter 和 D. P. Tew，J. Chem. Phys. 128, 224314（2008）]，对丙二醛的零点能和隧穿分裂进行了全维多组态含时哈特里计算。该势能面采用改进的 n 模式表示进行了近似，并进行了仔细的收敛性检查，以确保得到准确的结果。得到的分裂值（23.4 cm(-1)）与实验值 21.583 cm(-1)吻合良好。计算得到的零点能为 14670 cm(-1)，低于 Wang 等人的先前结果，但由于势能的 n 模式表示存在缺陷，可能低约 4 cm(-1)。本摘要中报告的能量包含了对忽略的振动角动量项的修正。
