Wang Yimin, Bowman Joel M
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
J Chem Phys. 2008 Sep 28;129(12):121103. doi: 10.1063/1.2978230.
We present tunneling calculations using the reaction path Hamiltonian in the zero-curvature approximation and a one-dimensional Hamiltonian in the imaginary-frequency, rectilinear normal mode of a saddle point, neglecting the vibrational angular momentum terms. This latter Hamiltonian was recently introduced and applied to the tunneling splitting in full-dimensional malonaldeyde [Y. Wang et al., J. Chem. Phys. 128, 224314 (2008)]. The results using the latter method are shown to be much more accurate than those using the former one for the ground-state tunneling splittings for H and D-transfer in malonaldehyde and for the D+H(2) reaction in three dimensions for zero total angular momentum.
我们给出了在零曲率近似下使用反应路径哈密顿量以及在鞍点的虚频直线型简正模式下使用一维哈密顿量的隧穿计算，忽略了振动角动量项。后一种哈密顿量最近被引入并应用于全维丙二醛中的隧穿分裂[Y. Wang等人，《化学物理杂志》128, 224314 (2008)]。结果表明，对于丙二醛中H和D转移的基态隧穿分裂以及三维空间中总角动量为零的D + H(2)反应，使用后一种方法得到的结果比使用前一种方法得到的结果要准确得多。
