Anomalous Λ-doubling in the infrared spectrum of the hydroxyl radical in helium nanodroplets
Date
2013
Authors
Raston, P.
Liang, T.
Douberly, G.
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Journal article
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The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2013; 117(34):8103-8110
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Paul L. Raston, Tao Liang, and Gary E. Douberly
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Abstract
The X2Π3/2 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 Λ-doublet splittings are determined to be 0.198(3) and 0.369(2) cm–1 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) Λ-doublet splitting was previously reported for the He solvated X2Π1/2 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 Λ-doublet splittings in He-solvated OH and NO. The model assumes a realistic parity dependence of the rotor’s effective moment of inertia and predicts a factor of 3.6 increase in the OH ground state (J = 3/2) Λ-doubling when the B0e and B0f rotational constants differ by less than one percent.
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© 2013 American Chemical Society