Conversion of Nuclear Spin Isomers of Ethylene

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 117; no. 39; pp. 9673 - 9683
• Main Authors: Chapovsky, P. L, Zhivonitko, V. V, Koptyug, I. V
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.10.2013
• Subjects: Conversion; Ethylene; Gas pressure; Grounds; Isomers; Nuclear spin; Physical chemistry; Rotational states
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp312322f

A theoretical model of the nuclear spin isomer conversion in C2H4 induced by the intramolecular spin–spin interaction between hydrogen nuclei has been developed. In the ground electronic state, C2H4 has four nuclear spin isomers in contrast to two isomers in the molecules studied so far in this field of research. At the gas pressure of 1 Torr, the rate of conversion between isomers with the nuclear spin symmetries B1u and B2u was found to be 5.2 × 10–4 s–1, which coincides within experimental uncertainties with the rate recently measured by Sun et al. ( Science 2005, 310, 1938 ). It was determined that at low gas pressures the conversion is induced mainly by the mixing of only one pair of rotational states. The calculated pressure dependence of the conversion rate predicts that conversion slows down with increasing pressure at pressures higher than 300 Torr.