Toward a precise determination of the acceptor switching splitting in the water dimer
Toward a precise determination of the acceptor switching splitting in the water dimer
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DOI：
10.1080/00268970601063812
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发表时间：
2007-03-01
影响因子：
1.7
通讯作者：
Saykally, R. J.
中科院分区：
文献类型：
--
作者：
Harker, H. A.;Keutsch, F. N.;Saykally, R. J.
精确测量水二聚体基态振动态的所有隧穿分裂对于完整而严格地确定分子间势能面是必不可少的。在这里，准确的实验确定的旋转常数和隧道分裂与基态受体转换（AS）分裂（H2O）（2）和（D2 O）（2）的估计相结合，以准确地预测指纹的弱允许E-2 E-1跃迁，并近似预测其绝对频率。虽然这些转变预计是相当弱的，目前的技术指导下，现在相当完整的水二聚体数据应该允许他们的观察。这些弱跃迁的测量将允许直接测定AS分裂，这是迄今为止逃避实验。
Precise measurement of all tunneling splittings in the ground vibrational state of the water dimer is essential for a complete and rigorous determination of the intermolecular potential energy surface. Here, accurate experimentally determined rotational constants and tunneling splittings were combined with estimates of the ground state acceptor switching (AS) splittings for both (H2O)(2) and (D2O)(2) in order to exactly predict the fingerprints of the weakly allowed E-2 E-1 transitions and to approximately predict their absolute frequencies. While these transitions are predicted to be quite weak, current technology guided by the now fairly complete water dimer data should permit their observation. The measurement of these weak transitions would permit the direct determination of AS splittings, which has so far eluded experiments.