The visible absorption spectrum of 1,2-cyclobutanedione in the gas phase

Abstract

The visible absorption spectrum of 1,2-cyclobutanedione has been measured in the gas phase at wavelengths between 4000 and 5100 Å. The absorption is attributed to the allowed π* ← n+, 1B1 ← 1A1 transition corresponding to the first excited singlet state. The spectrum shows a complex well-resolved vibrational structure which has been analysed, with some 125 bands measured and assigned. The bands at the longer wavelengths show sharp rotational fine structure, not yet analysed. The strongest band in the spectrum at 4933 Å has been assigned as the 0–0 band, while a band almost as strong at 4820 Å is attributed to excitation of one quantum of [Formula: see text], the a2 out-of-plane carbonyl bending vibration, and it is suggested that this band owes its intensity to vibronic coupling. A number of symmetric vibrations are also excited in the spectrum, but with no long progressions. Sequence bands running to the blue with an interval of about 72 cm−1 are prominent throughout the spectrum, and are assigned to v13, the a2 ring-twisting vibration. Other hot bands were also observed involving v13 which permitted estimation of energy levels for this vibration both in the ground state and the excited state. The infrared spectrum was also measured and analysed in the gas phase between 600 and 4000 cm−1, and 14 bands were assigned to fundamental vibrations; some of these assignments, at the lower frequencies, are uncertain.