Bulychev V P, Buturlimova M V, Tokhadze K G
Department of Physics, St. Petersburg State University , 7/9 Universitetskaya Nab., St. Petersburg 199034, Russian Federation.
J Phys Chem A. 2017 Sep 28;121(38):7255-7260. doi: 10.1021/acs.jpca.7b06517. Epub 2017 Sep 15.
The geometrical parameters, the frequencies, and absolute intensities of vibrational transitions of HO···trans-HONO hydrogen-bonded complex are calculated using the approach earlier tested in calculations of isolated molecules of nitrous acid and complexes of this acid with ammonia. The equilibrium nuclear configuration and potential energy and dipole moment surfaces are calculated by the MP2/aug-cc-pVTZ method with the basis set superposition error taken into account. The fundamental transition frequencies and intensities of the complex are first obtained in the harmonic approximation, and then the energy values, vibrational wave functions, and transition frequencies and intensities are determined from variational solutions of one- to four-dimensional anharmonic equations. The results obtained are compared with the data calculated in the same approximation for an isolated trans-HONO molecule and the NH···trans-HONO complex. The average discrepancy between the anharmonic frequency values and five available experimental data is 15 cm. Three absorption bands of trans-HONO with the highest intensity are recommended for detecting the presence of HO···trans-HONO.
采用之前在亚硝酸孤立分子及其与氨的配合物计算中测试过的方法，计算了HO···反式-HONO氢键复合物的几何参数、振动跃迁频率和绝对强度。通过MP2/aug-cc-pVTZ方法计算平衡核构型、势能和偶极矩曲面，并考虑基组叠加误差。首先在简谐近似下获得复合物的基本跃迁频率和强度，然后从一到四维非谐方程的变分解确定能量值、振动波函数以及跃迁频率和强度。将所得结果与在相同近似下计算的孤立反式-HONO分子和NH···反式-HONO配合物的数据进行比较。非谐频率值与五个现有实验数据之间的平均差异为15 cm。推荐反式-HONO强度最高的三个吸收带用于检测HO···反式-HONO的存在。
