Wang Yimin, Bowman Joel M
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
J Phys Chem Lett. 2015 Jan 2;6(1):124-8. doi: 10.1021/jz5022944. Epub 2014 Dec 18.
Using a new potential energy surface, based on fitting around 33,000 CCSD(T)-F12/aug-cc-pVTZ energies, a robust set of predictions is made for mode-specific isomerization of trans-hydroxymethylene to formaldehyde in the deep tunneling region. The calculations make use of a recent projection model for mode-specific tunneling based on the rectilinear Q(im) path [ Wang , Y. ; Bowman , J. M. J. Chem. Phys. 2013 , 139 , 154303 ]. The most interesting prediction is a large decrease in the half-life from roughly 5 h for the ground vibrational state to roughly 1.5 min and 1 s by excitation of the fundamental and first overtone of the asymmetric bending normal mode, respectively. The properties of the new PES are described along with variational calculations of low-lying vibrational states of trans- and cis-hydroxymethylene.
基于对约33000个CCSD(T)-F12/aug-cc-pVTZ能量进行拟合，利用新的势能面，对深隧穿区域中反式羟基亚甲基向甲醛的模式特异性异构化进行了一组可靠的预测。计算使用了基于直线Q(im)路径的最近的模式特异性隧穿投影模型[王，Y.；鲍曼，J. M.《化学物理杂志》2013年，139卷，154303页]。最有趣的预测是，通过激发不对称弯曲简正模式的基频和第一泛频，半衰期从基态振动的大约5小时大幅降至大约1.5分钟和1秒。同时描述了新势能面的性质以及反式和顺式羟基亚甲基低能级振动态的变分计算。
