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Low frequency vibrational anharmonicity and nuclear spin effects of Cl-(H2) and Cl-(D2)

Abstract : Low frequency combination bands of 35Cl-(H2) and 35Cl-(D2) have been measured in the region between 600 and 1100 cm-1 by infrared predissociation spectroscopy in a cryogenic 22-pole ion trap using a free electron laser at the FELIX Laboratory as a tunable light source. The 35Cl-(H2) (35Cl-(D2)) spectrum contains three bands at 773 cm-1 (620 cm-1), 889 cm-1 (692 cm-1), and 978 cm-1 (750 cm-1) with decreasing intensity toward higher photon energies. Comparison of the experimentally determined transition frequencies with anharmonic vibrational self-consistent field and vibrational configuration interaction calculations suggests the assignment of the combination bands v1 + v2, 2v1 + v2, and 3v1 + v2 for 35Cl-(H2) and 2v1 + v2, 3v1 + v2, and 4v1 + v2 for 35Cl-(D2), where v1 is the 35Cl-⋯H2 stretching fundamental and v2 is the Cl-(H2) bend. The observed asymmetric temperature dependent line shape of the v1 + v2 transition can be modeled by a series of ∑+-∏ ro-vibrational transitions, when substantially decreasing the rotational constant in the vibrationally excited state by 35%. The spectrum of 35Cl-(D2) shows a splitting of 7 cm-1 for the strongest band which can be attributed to the tunneling of the ortho/para states of D2.
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Submitted on : Wednesday, May 25, 2022 - 11:18:37 AM
Last modification on : Monday, July 4, 2022 - 10:27:02 AM

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Steffen Spieler, Dennis F. Dinu, Pavol Jusko, Björn Bastian, Malcolm Simpson, et al.. Low frequency vibrational anharmonicity and nuclear spin effects of Cl-(H2) and Cl-(D2). The Journal of Chemical Physics, 2018, 149, ⟨10.1063/1.5049680⟩. ⟨insu-03678161⟩

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