THE ARGON-ACETALDEHYDE VAN DER WAALS COMPLEX SPECTRUM, STRUCTURE, DIPOLE MOMENT, AND TUNNELING MOTIONS

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1993

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Ohio State University

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166 transitions of the argon-acctaldchyde complex have been observed by FTMW spectroscopy. The transitions appear in quartets centered near the rigid rotor frequencies. The overall splitting in the a and b transitions is about 1-3 MHz. The c-type transitions appear as two doublets symmetrically shifted from the rigid rotor frequencies by about ±200 MHz. Each line is split by methyl rotation in the acetaldehyde, while the additional doubling is attributed to an inversion tunneling motion through a planar configuration. Frequencies were matched by sum rules to experimental accuracy, in order to identify the level structure. They show each rigid rotor level being split into four states, two A and two E. Averaging of the two A-states and subsequent fitting to a rigid rotor Hamiltonian yields the following rotational constants; A=9306MHz,B=1806MHz,C=1570MHz. Substitution of the acetaldehyde hydrogen by deuterium and fitting as above yields the additional rotational constants; A=9035MHz,B=1767MHz,C=1550MHz. These six parameters determine the position of the Argon as approximately Rcm=3.59(1) {\AA}, RArO=3.6(2) {\AA}, RArCm=3.7(2) {\AA}. The complex is nonplanar and the argon is located above the C-C-O triangle. Since the system exhibits multi-dimensional tunneling, the Hougen-Coudert formalism is being employed to fit the spectrum. A program is currently being written in consultation with Dr. J.T. Hougen to implement the formalism for this particular case, and the interpretation is based on the G6 group. The correlation of the group to C1 suggests that each rigid rotor level should be split into four states, A1+A2+2E, as observed.

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Author Institution: Department of Chemistry, University of Michigan

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