Université Paris-Est, Laboratoire Modélisation et Simulation Multi-Echelle (MSME), UMR 8208 CNRS, 5 bd Descartes, 77454 Marne la Vallée, France.
J Chem Phys. 2012 Jul 7;137(1):014306. doi: 10.1063/1.4732150.
We present numerically exact vibrational transitions for trans-HOCO, cis-HOCO, and cis-HOCO(-) for the quartic force fields of Fortenberry et al. [J. Chem. Phys. 135, 134301 (2011); ibid. 135, 214303 (2011)], obtained by means of a computational strategy based on the discrete variable representation. Several adiabatic projection schemes have been employed to characterize the vibrational levels and to study the relevance of the intermode coupling (vibrational mixing). Our results help to clear up a large discrepancy between previously reported vibrational perturbation theory and vibrational configuration interaction predictions for the torsional frequency.
我们给出了 Fortenberry 等人[J. Chem. Phys. 135, 134301 (2011); ibid. 135, 214303 (2011)]提出的四次力场中反式-HOCO、顺式-HOCO 和顺式-HOCO(-)的振动跃迁的数值精确结果，该力场是通过基于离散变量表示的计算策略获得的。我们采用了几种绝热投影方案来描述振动能级，并研究了模态耦合（振动混合）的相关性。我们的结果有助于澄清先前报道的扭转频率的振动微扰理论和振动构型相互作用预测之间的一个大分歧。
