Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
J Chem Phys. 2011 Dec 28;135(24):244304. doi: 10.1063/1.3671459.
Collisional energy transfer kinetics of vibrationally excited acetylene has been examined for states with internal energies near 6560 cm(-1). Total population removal rate constants were determined for selected rotational levels of the (1,0,1,0(0),0(0)) and (0,1,1,2(0),0(0)) states. Values in the range of (10-18) × 10(-10) cm(3) s(-1) were obtained. Measurements of state-to-state rotational energy transfer rate constants were also carried out for these states. The rotational energy transfer kinetics was found to be consistent with simple energy gap models for the transfer probabilities. Vibrational transfer out of the (0,1,1,2(0),0(0)) state accounted for no more than 16% of the total removal process. Transfer from (1,0,1,0(0),0(0)) to the u-symmetry (0,2,0,3(1),1(-1)), (0,1,1,2(0),0(0)), and (1,1,0,1(1),1(-1)) states was observed. Applying the principle of detailed balance to these data indicated that vibrational transfer to (1,0,1,0(0),0(0)) accounted for ~0.1% of the population loss from (0,2,0,3(1),1(-1)) or (0,1,1,2(0),0(0)), and 3% of the loss from (1,1,0,1(1),1(-1)). Relative rotational transfer probabilities were obtained for transfer to the g-symmetry (1,1,0,2(0),0(0))∕(0,0,2,0(0),0(0)) dyad. These results are related to recent studies of optically pumped acetylene lasers.
已研究了振动乙炔的碰撞能量转移动力学，其内部能量接近 6560 cm(-1)。为 (1,0,1,0(0),0(0)) 和 (0,1,1,2(0),0(0)) 态的选定转动能级确定了总布居去除率常数。在 (10-18) × 10(-10) cm(3) s(-1) 的范围内获得了这些值。还对这些态的态间转动能量转移率常数进行了测量。发现转动能量转移动力学与转移概率的简单能量隙模型一致。从 (0,1,1,2(0),0(0)) 态振动转移不超过总去除过程的 16%。从 (1,0,1,0(0),0(0)) 到 u 对称 (0,2,0,3(1),1(-1))、(0,1,1,2(0),0(0)) 和 (1,1,0,1(1),1(-1)) 态的转移被观察到。将详细平衡原理应用于这些数据表明，振动转移到 (1,0,1,0(0),0(0)) 占从 (0,2,0,3(1),1(-1)) 或 (0,1,1,2(0),0(0)) 损失的布居的~0.1%，以及从 (1,1,0,1(1),1(-1)) 损失的 3%。对于转移到 g 对称 (1,1,0,2(0),0(0))∕(0,0,2,0(0),0(0)) 偶极子，获得了相对转动转移概率。这些结果与最近的光学泵浦乙炔激光器研究有关。
