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J Phys Chem A. 2013 Oct 3;117(39):9753-60. doi: 10.1021/jp3124023. Epub 2013 Apr 10.

Microwave studies on 1,4-pentadiene: CH2═CH-CH2-CH═CH2; transformations among the three rotational isomers.

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1
The Graduate University for Advanced Studies , Hayama, Kanagawa 240-0193, Japan.

Abstract

In order to examine significant roles of conformations played in various research fields, a molecule with two internal-rotation axes of high symmetry, 1,4-pentadiene, was studied in detail through the observation of its rotational spectra by using various types of microwave spectroscopy, Stark modulation and Fourier transform in the centimeter-wave region, direct absorption in the millimeter-wave region, and centimeter-/millimeter-wave combinations for double resonance, along with ab initio molecular orbital calculations. The molecule was confirmed to exist in three rotameric forms: skew-skew, cis-skew, and skew-skew'. For the cis-skew form, rotational spectra not only in the ground vibrational state, but also in three excited C-C torsional states were detected. Rotational and centrifugal distortion constants were precisely determined by the analysis of all the observed spectra, in addition to the relative energies of the three isomers and the torsional frequencies for the cis-skew form, as estimated from the observed spectral line intensities. The skew-skew form was found to be the most stable among the three isomers, the cis-skew form higher in energy than the skew-skew by 172 ± 66 cm(-1), and the skew-skew' form higher in energy than the cis-skew by 44 ± 26 cm(-1). These experimental results were compared with those derived from a two-dimensional potential energy surface calculated by ab initio molecular orbital methods, in order to obtain a global view of molecular dynamics taking place on the surface, while paying attention to unique features of internal rotation characteristic of two dimensions.

PMID:
23488862
DOI:
10.1021/jp3124023
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