Mabbs Richard, Pichugin Kostyantyn, Sanov Andrei
Department of Chemistry, University of Arizona, Tucson, 85721-0041, USA.
J Chem Phys. 2005 May 1;122(17):174305. doi: 10.1063/1.1887170.
Time-resolved photoelectron imaging of negative ions is employed to study the dynamics along the reaction coordinate in the photodissociation of IBr(-). The results are discussed in a side-by-side comparison with the dissociation of I(2) (-), examined under similar experimental conditions. The I(2) (-) anion, extensively studied in the past, is used as a reference system for interpreting the IBr(-) results. The data provide rigorous dynamical tests of the anion electronic potentials. The evolution of the energetics revealed in the time-resolved (780 nm pump, 390 nm probe) I(2) (-) and IBr(-) photoelectron images is compared to the predictions of classical trajectory calculations, with the time-resolved photoelectron spectra modeled assuming a variety of neutral states accessed in the photodetachment. In light of good overall agreement of the experimental data with the theoretical predictions, the results are used to construct an experimental image of the IBr(-) dissociation potential as a function of the reaction coordinate.
利用负离子的时间分辨光电子成像技术来研究IBr(-)光解离过程中沿反应坐标的动力学。将这些结果与在相似实验条件下研究的I(2) (-)的解离进行并列比较讨论。过去对I(2) (-)阴离子进行了广泛研究，它被用作解释IBr(-)结果的参考体系。这些数据为阴离子电子势提供了严格的动力学测试。将时间分辨（780纳米泵浦，390纳米探测）I(2) (-)和IBr(-)光电子图像中揭示的能量学演变与经典轨迹计算的预测进行比较，同时对时间分辨光电子能谱进行建模，假设在光剥离过程中可以进入多种中性状态。鉴于实验数据与理论预测总体上吻合良好，这些结果被用于构建作为反应坐标函数的IBr(-)解离势的实验图像。
