The microwave spectrum of gauche-ethylamine |
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Authors: | E. Fischer I. Botskor |
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Affiliation: | Department of Chemistry, University of Ulm, D-7900 Ulm, West Germany |
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Abstract: | The microwave spectrum of the ground state of the normal species of gauche-ethylamine CH3CH2NH2 and that of -NHD, -NDH, as well as -ND2 isotopic species were measured and assigned. The ground state splits into four substates due to two internal large amplitude motions: inversion (s and a) and internal rotation (o and e) about the CN axis. Intersystem transitions due to tunneling as well as vibrational-rotational perturbations affect not only the absorption frequencies but also the Stark effect and NQHFS. The rotational constants for the two symmetrical inversion states (s) were fitted for the normal species as (all values in MHz) Ase = 32 423.470 ± 0.184, Bse = 8 942.086 ± 0.039, and Cse = 7 825.520 ± 0.048, and Aso = 32 378.733 ± 0.182, Bso = 8 940.906 ± 0.052, and Cso = 7 825.551 ± 0.042 with the interaction constants Qas = 151.12 ± 0.52 and Qbs = 44.4 ± 7.0. The antisymmetrical inversion states (a) were fitted as Aae = 32 423.347 ± 0.142, Bae = 8 942.027 ± 0.029, and Cae = 7 825.525 ± 0.031, and Aao = 32 378.720 ± 0.142, Bao = 8 940.984 ± 0.029, and Cao = 7 825.573 ± 0.031 with the interaction constants Qaa = 167.10 ± 0.31, Qba = 48.1 ± 5.4. The energy splitting due to intersion was determined (in MHz) as Δνinv = 1 391.39 ± 0.19 and that due to internal rotation as Δνtors = 1 170.58 ± 0.18. The cis barrier separating the two equivalent torsional states was calculated as 690 cm?1, and the inversion barrier between the inversion states was calculated as 1400 cm?1, both using the Dennison-Uhlenbeck model. A simple model explaining the inversion splittings of the monodeuterated species is proposed. Comparing the relative intensities for several temperatures the gauche form was observed to be energetically higher than the trans form by 110 ± 50 cm?1. The dipole moment could only be fitted by taking into account the internal motions yielding (in Debye) μaeff = 0.11 ± 0.01, μbeff = 0.65 ± 0.01, and μceff = 1.014 ± 0.015. The quadrupole coupling constants (in MHz) were found as χaa = ?χ+ = 2.268 ± 0.043 and χbb ? χcc = χ? = 3.120 ± 0.035. |
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