Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.
J Chem Phys. 2009 Nov 21;131(19):194301. doi: 10.1063/1.3262715.
Two new electronic transition systems, namely, the 14.0Phi(7/2)-Chi (2)Delta(5/2) and the 15.7Phi(5/2)-Chi (2)Delta(5/2) transitions were observed and analyzed using laser vaporization/reaction supersonic free jet expansion and high resolution laser induced fluorescence spectroscopy. In addition, the (v, 0) bands with v=6-10 of the 14.6Delta(5/2)-Chi (2)Delta(5/2) transition were found to be perturbed by the 15.7Phi(5/2) state. The interaction between the 14.6Delta(5/2) and the 15.7Phi(5/2) states is evident in the progressive increase in hyperfine width of rotational lines of the 14.6Delta(5/2)-X (2)Delta(5/2) transition as the vibrational quantum number increases. Deperturbation procedures were successfully applied to analyze the interaction between these two states. All observed spectra show partially resolved hyperfine structure, and the hyperfine width decreases rapidly as J increases suggested that the hyperfine structure conforms to the Hund's case a(beta) coupling scheme. Accurate molecular and hyperfine constants for the 14.0Phi(7/2), the 14.6Delta(5/2) and the 15.7Phi(5/2) states were obtained and analyzed.
两个新的电子跃迁系统，即14.0Phi(7/2)-Chi (2)Delta(5/2)和15.7Phi(5/2)-Chi (2)Delta(5/2)跃迁，是通过激光蒸发/反应超声速自由喷射扩展和高分辨率激光诱导荧光光谱学观察和分析的。此外，还发现[v，0]带（v=6-10）的14.6Delta(5/2)-Chi (2)Delta(5/2)跃迁受到15.7Phi(5/2)态的干扰。14.6Delta(5/2)和15.7Phi(5/2)态之间的相互作用，在[v，0]带（v=6-10）的14.6Delta(5/2)-Chi (2)Delta(5/2)跃迁的旋转线的超精细宽度随着振动量子数的增加而逐渐增加，这是显而易见的。去微扰程序成功地应用于分析这两个状态之间的相互作用。所有观察到的光谱都显示出部分分辨的超精细结构，并且随着 J 的增加，超精细宽度迅速减小，这表明超精细结构符合 Hund's case a(beta)耦合方案。准确的分子和超精细常数为14.0Phi(7/2)、14.6Delta(5/2)和15.7Phi(5/2)态被获得和分析。
