Accurate bond dissociation energy of water determined by triple-resonance vibrational spectroscopy and ab initio calculations
Accurate bond dissociation energy of water determined by triple-resonance vibrational spectroscopy and ab initio calculations
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DOI：
10.1016/j.cplett.2013.03.007
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发表时间：
2013-05-01
影响因子：
2.8
通讯作者：
Polyansky, Oleg L.
中科院分区：
文献类型：
--
作者：
Boyarkin, Oleg V.;Koshelev, Maxim A.;Polyansky, Oleg L.
三重共振振动光谱用于确定水同位素体（HDO）-O-16的最低解离能Do为41239.7 +/- 0.2 cm（-1），并将（H2O）-O-16的D-0提高到41145.92 +/- 0.12 cm（-1）。包括系统基组和电子相关收敛研究、相对论和兰姆位移效应以及超出Born-Oppenheimer近似的修正在内的从头计算结果分别与测量值一致到1和2 cm（-1）。高阶相关项的改进处理是这种高理论精度的关键。预计其他五种主要水同位素的D-0预测值在1 cm（-1）以内是正确的。(C)2013 Elsevier B. V.保留所有权利。
Triple-resonance vibrational spectroscopy is used to determine the lowest dissociation energy, Do, for the water isotopologue (HDO)-O-16 as 41239.7 +/- 0.2 cm(-1) and to improve D-0 for (H2O)-O-16 to 41 145.92 +/- 0.12 cm(-1). Ab initio calculations including systematic basis set and electron correlation convergence studies, relativistic and Lamb shift effects as well as corrections beyond the Born-Oppenheimer approximation, agree with the measured values to 1 and 2 cm(-1) respectively. The improved treatment of high-order correlation terms is key to this high theoretical accuracy. Predicted values for D-0 for the other five major water isotopologues are expected to be correct within 1 cm(-1). (C) 2013 Elsevier B.V. All rights reserved.