Senent M L, Fernández-Herrera S, Smeyers Y G
Departamento de Física y Química Teóricas, I. Estructura de la Materia, C.S.I.C., Madrid, Spain.
Spectrochim Acta A Mol Biomol Spectrosc. 2000 Jul;56A(8):1457-68. doi: 10.1016/s1386-1425(99)00267-x.
In the present paper, the roto-torsional energy levels of hydrogen peroxide are determined from ab initio calculations performed at the MP4(SDQ)/AUG-cc-pVTZ//MP4(SDQ)/cc-pVTZ+ ++ level. The rotational levels corresponding to the torsional states n = 0 and 1 are determined variationally up to J = 20. The flexible model used considers the roto-vibrational interactions. Symmetry conditions are included for classifying the levels and reducing the cost of diagonalization. Products of contracted torsional basis functions and top symmetric solutions are employed as basis functions. The calculated levels are in a very good agreement with the experimental data. In addition, the K-doubling has been obtained and the levels fitted to the top symmetric equations for determining the centrifugal distortion constants. The expectation values of the rotational constants at the lowest torsional levels are compared with the rotational constants arising from the experimental fit.
在本文中，过氧化氢的旋转扭转能级由在MP4(SDQ)/AUG-cc-pVTZ//MP4(SDQ)/cc-pVTZ +++水平上进行的从头计算确定。对应于扭转态n = 0和1的转动能级在变分法下确定到J = 20。所使用的灵活模型考虑了旋转振动相互作用。为能级分类和降低对角化成本纳入了对称条件。采用收缩扭转基函数与陀螺对称解的乘积作为基函数。计算得到的能级与实验数据非常吻合。此外，获得了K-双重分裂，并将能级拟合到陀螺对称方程以确定离心畸变常数。将最低扭转能级处转动常数的期望值与实验拟合得到的转动常数进行了比较。
