Anomalous 螞-Doubling in the Infrared Spectrum of the Hydroxyl Radical in Helium Nanodroplets

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• 作者：Paul L. Raston ; Tao Liang ; Gary E. Douberly
• 刊名：Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：August 29, 2013
• 年：2013
• 卷：117
• 期：34
• 页码：8103-8110
• 全文大小：352K
• 年卷期：v.117,no.34(August 29, 2013)
• ISSN：1520-5215

文摘

The X²螤_3/2 hydroxyl (OH) radical has been isolated in superfluid ⁴He nanodroplets and probed with infrared laser depletion spectroscopy. From an analysis of the Stark spectrum of the Q(3/2) transition, the 螞-doublet splittings are determined to be 0.198(3) and 0.369(2) cm^鈥? in the ground and first excited vibrational states, respectively. These splittings are 3.6 and 7.2 times larger than their respective gas phase values. A factor of 1.6 increase in the Q(1/2) 螞-doublet splitting was previously reported for the He solvated X²螤_1/2 NO radical [von Haeften, K.; Metzelthin, A.; Rudolph, S.; Staemmler, V.; Havenith, M. Phys. Rev. Lett. 2005, 95, 215301]. A simple model is presented that reproduces the observed 螞-doublet splittings in He-solvated OH and NO. The model assumes a realistic parity dependence of the rotor鈥檚 effective moment of inertia and predicts a factor of 3.6 increase in the OH ground state (J = 3/2) 螞-doubling when the B₀^e and B₀^f rotational constants differ by less than one percent.