Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, USA.
J Chem Phys. 2009 Dec 14;131(22):224311. doi: 10.1063/1.3270160.
The difluorothiophosphoryl (F(2)PS) free radical has been produced in a supersonic discharge jet from a precursor mixture of F(3)PS and high pressure argon and detected by laser-induced fluorescence and single vibronic level emission spectroscopy. With the aid of high level ab initio predictions of the properties of the ground and first two excited doublet states, the observed band system has been positively identified as B(2)A(')-X(2)A('). The electronic transition involves promotion of an electron from the pi to the pi( *) orbital with concomitant increases in the out-of-plane angle and PS bond length on excitation. The observed vibrational structure, Franck-Condon profile, rotational band contours, T(0) energy, and ground and excited state vibrational frequencies are all in accord with expectations based on our theoretical predictions.
二氟硫膦基（F(2)PS）自由基已在超音速放电射流中从 F(3)PS 和高压氩气的前体混合物中产生，并通过激光诱导荧光和单振子能级发射光谱进行检测。借助对基态和前两个激发双重态性质的高级别从头预测，观察到的带系已被确认为 B(2)A(')-X(2)A(')。电子跃迁涉及从π到π(*)轨道的电子激发，同时平面外角和 PS 键长增加。观察到的振动结构、Franck-Condon 轮廓、转动带轮廓、T(0)能量以及基态和激发态振动频率都与我们的理论预测相符。
