Schofield Daniel P, Kjaergaard Henrik G, Matthews Jamie, Sinha Amitabha
Department of Chemistry, University of Otago, P.O. Box 56, Dunedin, New Zealand.
J Chem Phys. 2005 Oct 1;123(13):134318. doi: 10.1063/1.2047574.
We have simulated the HOONO vibrational overtone spectrum with use of a local mode Hamiltonian that includes the OH-stretching, OOH-bending, and NOOH-torsional modes and coupling between all three modes. The local mode parameters and the dipole moment function are calculated with coupled-cluster ab initio theory and an augmented Dunning-type triple-zeta basis set. We investigate the accuracy of the local mode parameters obtained from two different potential-energy fitting routines, as well as the sensitivity of these parameters to the basis set employed. We compare our simulated spectra to previously published action spectra in the first and second OH-stretching overtone regions. In addition we have recorded the spectrum in the OH-stretch and OOH-bend combination region around 7700 cm-1 and we also compare to this. Our simulated spectrum is in qualitative agreement with experiment in the first and second OH-stretching overtone and in the stretch-bend regions.
我们使用了一个局域模哈密顿量来模拟HOONO振动泛频光谱，该哈密顿量包括OH伸缩、OOH弯曲和NOOH扭转模式以及这三种模式之间的耦合。局域模参数和偶极矩函数是通过耦合簇从头算理论和一个增强的邓宁型三重ζ基组计算得到的。我们研究了从两种不同的势能拟合程序获得的局域模参数的准确性，以及这些参数对所采用基组的敏感性。我们将模拟光谱与先前发表的第一和第二OH伸缩泛频区域的作用光谱进行了比较。此外，我们记录了在7700 cm-1附近的OH伸缩和OOH弯曲组合区域的光谱，并也进行了比较。我们的模拟光谱在第一和第二OH伸缩泛频以及伸缩弯曲区域与实验结果在定性上是一致的。
