Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, La Jolla, California 92093-0340, USA.
J Phys Chem A. 2010 Jan 28;114(3):1485-91. doi: 10.1021/jp907480y.
Translational spectroscopy has been used to study the dissociation of HOCO and DOCO to both the OH/OD(X(2)Pi) + CO(X(1)Sigma(+)) and H/D((2)S) + CO(2)(X(1)Sigma(+)) product channels upon charge exchange between a fast (keV) beam of HOCO(+)/DOCO(+) and cesium. Analysis of the measured kinetic energy release distributions for the two product channels suggests that HOCO is initially produced in the 1(2)A'' electronic state by near resonant electron capture from cesium (approximately 4.31 eV above the ground state trans-HOCO conformer). This initial state undergoes rapid predissociation leading to OH + CO and H + CO(2) products, with respective branching fractions of 0.75 +/- 0.03 and 0.25 +/- 0.03. Possible mechanisms leading to dissociation and the observed dissociation dynamics are presented in light of theoretical studies of the low-lying electronic states of HOCO.
转译光谱学已被用于研究 HOCO 和 DOCO 在与铯的电荷交换作用下通过两种产物通道解离的情况，这两种产物通道分别为 OH/OD(X(2)Pi) + CO(X(1)Sigma(+)) 和 H/D((2)S) + CO(2)(X(1)Sigma(+))。对两种产物通道的测量动能释放分布的分析表明，HOCO 最初由铯（约高于基态反式 HOCO 构象的 4.31 eV）的近共振电子俘获产生于 1(2)A''电子态。这个初始态会迅速进行预解离，生成 OH + CO 和 H + CO(2)产物，相应的分支比分别为 0.75 +/- 0.03 和 0.25 +/- 0.03。在考虑 HOCO 低能电子态的理论研究的基础上，提出了导致解离的可能机制和观察到的解离动力学。
