Ritz assignment and Watson fits of the high-resolution ring-puckering spectrum of oxetane |
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Authors: | Giovanni Moruzzi Brenda P Winnewisser Manfred Winnewisser |
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Institution: | a Dipartimento di Fisica “Enrico Fermi” dell’Università di Pisa and INFM, Via F. Buonarroti 2, Pisa I-56127, Italy b Physikalisch-Chemisches Institut, Justus-Liebig-Universität, Heinrich-Buff-Ring 58, Giessen D-35392, Germany c Institut für Physikalische Chemie der Georg-August-Universität Göttingen, Tammanstrasse 6, Göttingen D-37077, Germany d Department of Physics, The Ohio State University, 174 West 18th Avenue, Columbus, OH 43210-1106, USA |
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Abstract: | Oxetane is a four-membered ring molecule exhibiting a large-amplitude ring-puckering motion. In order to analyze this vibration we recorded a rotationally resolved far-infrared spectrum between 50 and 145 cm−1. The analysis of the ring-puckering fundamental band with the assignment of 1108 lines, has been presented in a previous paper. In the present work we present a list of further 6531 assigned transitions between the five lowest excited ring-puckering states. The 4983 term values involved in the transitions assigned in this and in the preceding work have been evaluated by the “Ritz” program, and are now available. An A-reduced Watson Hamiltonian in any of the three representations Ir, IIr, and IIIr was used to perform a fit of the assigned transitions. Precise rotational constants and quartic as well as a full set of sextic centrifugal distortion constants were obtained for the investigated ring-puckering states. For the first time, high-resolution values for the vibrational Gv parameters have been obtained, and we have added terms in x6 and x8 to the double minimum-potential well describing the ring-puckering motion, in order to reproduce their values within the experimental accuracy. The same potential still reproduces the lower resolution values of the Q-branch origins involving higher ring-puckering states up to vrp=14 found in the previous literature. |
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Keywords: | Ring puckering High-resolution far-infrared spectroscopy Large-amplitude motion Oxetane |
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