Ultraviolet Cavity Ringdown Spectra and the S sub(1)(n,pi) Ring-Inversion Potential Energy Function for 2-Cyclohexen-1-one-d sub(0) and Its 2,6,6- d sub(3) Isotopomer

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 112; no. 1; pp. 38 - 44
• Main Authors: Rishard, Mohamed ZM, Brown, Elizabeth A, Ausman, Logan K, Drucker, Stephen, Choo, Jaebum, Laane, Jaan
• Format: Journal Article
• Language: English
• Published: 01.01.2008
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp075281c

The cavity ringdown spectra of 2-cyclohexen-1-one (2CHO) and its 2,6,6- d sub(3) isotopomer (2CHO-d sub(3)) have been recorded in the spectral region near their S sub(1)(n,pi)larrS sub(0) band origins which are at 26 081.3 and 26 075.3 cm super(-1), respectively. The data allow several of the quantum states of nu sub(39), the ring inversion, to be determined for both the ground and excited electronic states. These were utilized to calculate the one- dimensional potential energy functions which best fit the data. The barriers to inversion for the S sub(0) and S sub(1)(n,pi) states were found to be 1900 plus or minus 300 and 3550 plus or minus 500 cm super(-1), respectively. Density functional theory calculations predict values of 2090 and 2265 cm super(-1), respectively.