Department of Chemistry, Laser Spectroscopy Facility, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, USA.
J Chem Phys. 2009 Nov 14;131(18):184303. doi: 10.1063/1.3262612.
We have recorded high resolution, partially rotationally resolved, jet-cooled cavity ringdown spectra of the origin band of the A-X electronic transition of both the G and T conformers of the perproteo and perdeutero isotopologues of the ethyl peroxy radical, C(2)H(5)O(2). This transition, located in the near infrared, was studied using a narrow band laser source (< or approximately 250 MHz) and a supersonic slit-jet expansion coupled with an electric discharge allowing us to obtain rotational temperatures of about 15 K. All four spectra have been successfully simulated using an evolutionary algorithm approach with a Hamiltonian including rotational and spin-rotational terms. Excellent agreement with the experimental spectra was obtained by fitting seven molecular parameters in each ground and the first excited electronic states as well as the band origin of the electronic transition. This analysis unambiguously confirms the assignment of the lower frequency origin band to the G conformer and the higher frequency one to the T conformer.
我们已经记录了高分辨率、部分旋转分辨的喷射冷却腔衰减光谱，其中包括 G 和 T 构象的过氧乙基自由基（C(2)H(5)O(2)）的 A-X 电子跃迁的原始带的全氘代和氚代同位素。该跃迁位于近红外区域，使用窄带激光源（<或大约 250 MHz）和超音速狭缝喷射扩展与放电相结合进行了研究，这使我们能够获得约 15 K 的转动温度。使用包括转动和自旋-转动项的哈密顿量的演化算法方法，成功地模拟了所有四个光谱。通过在每个基态和第一激发电子态以及电子跃迁的带原点拟合七个分子参数，与实验光谱获得了极好的一致性。这种分析明确证实了较低频率原始带的归属为 G 构象，而较高频率的归属为 T 构象。
