Flaud J, Birk M, Wagner G, Orphal J, Klee S, Lafferty WJ
Bâtiment 210-, UniversitéParis-Sud, Orsay, 91405, France
J Mol Spectrosc. 1998 Oct;191(2):362-367. doi: 10.1006/jmsp.1998.7653.
The far infrared spectrum of HOCl has been recorded at high resolution between 20 and 360 cm-1 by means of Fourier transform spectroscopy, and it was possible to observe pure rotation lines involving rotational levels with high Ka quantum numbers (up to Ka = 9). These lines combined with microwave and tunable far infrared data available in the literature were least squares fitted using a Watson-type Hamiltonian. The fitting leads to precise sets of rotational and centrifugal distortion constants for the ground states of both isotopomers HO35Cl and HO37Cl. Also relative line intensities were measured and their fitting allowed the determination of rotational corrections to the b-component of the permanent transition moment. Finally, to get Hamiltonian constants consistent with the newly determined ground state constants for the (100), (010), (001) vibrational states, available data concerning the nu1, nu2, and nu3 bands were refitted. Three interesting points are to be stressed. For the (001) state, we were able to complete the existing data with rotation lines observed in our spectra up to rather high Ka values (Ka = 7). For HO35Cl, we were able to show that some (010) and (100) levels are perturbed by levels of the (002) and (030) states, respectively, through Coriolis-type interactions. This allows the determination of the band centers of these two dark states. Copyright 1998 Academic Press.
利用傅里叶变换光谱法在20至360厘米⁻¹的高分辨率下记录了HOCl的远红外光谱，并且有可能观测到涉及高Ka量子数（高达Ka = 9）转动能级的纯转动谱线。这些谱线与文献中可用的微波和可调谐远红外数据相结合，使用沃森型哈密顿量进行了最小二乘法拟合。拟合得出了两种同位素异构体HO³⁵Cl和HO³⁷Cl基态精确的转动常数和离心畸变常数集。还测量了相对谱线强度，对其进行拟合使得能够确定对永久跃迁矩b分量的转动修正。最后，为了获得与新确定的(100)、(010)、(001)振动态基态常数一致的哈密顿常数，对有关ν₁、ν₂和ν₃带的现有数据进行了重新拟合。需要强调三个有趣的点。对于(001)态，我们能够用在我们的光谱中观测到的高达相当高Ka值（Ka = 7）的转动谱线来补充现有数据。对于HO³⁵Cl，我们能够表明一些(010)和(100)能级分别通过科里奥利型相互作用受到(002)和(030)态能级的微扰。这使得能够确定这两个暗态的带中心。版权所有1998年学术出版社。
