Intermolecular Vibration Coupling between Libration of Water and 谓2-SOH for Clusters HSO4鈥?/sup>(H2O)n
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- 作者：Jing-Jing Yu ; Yun-Hong Zhang ; Ze-Sheng Li
- 刊名：The Journal of Physical Chemistry B
- 出版年：2012
- 出版时间：October 18, 2012
- 年：2012
- 卷：116
- 期：41
- 页码：12597-12604
- 全文大小：445K
- 年卷期：v.116,no.41(October 18, 2012)
- ISSN：1520-5207
文摘
The hydrated bisulfate ion clusters (HSO4鈥?/sup>(H2O)n, n = 1鈥?0) were optimized at the M06/6-311++G(d,p) level. The factors affecting 谓2-SOH of the clusters involved vibration coupling between 谓2-SOH and the water wagging libration mode (W-H2O) and hydrogen bonding effect. In order to understand the vibration coupling between W-H2O and 谓2-SOH for the bisulfate clusters, D2O instead of H2O and Se instead of S were used to estimate the uncoupling frequency of 谓2-SOH and W-H2O, respectively. For HSO4鈥?/sup>路H2O-I, the uncoupling frequencies of 谓2-SOH and W-H2O were obtained at 752.0 and 753.4 cm鈥?. After coupling, the frequencies appeared at 782.2 and 732.6 cm鈥?. H2S and NH4+ instead of D2O in HSO4鈥?/sup>路D2O-II were compared to analyze the effect of hydrogen bond. The sequence of hydrogen bond strength was found to be HSO4鈥?/sup>路H2S-II < HSO4鈥?/sup>路D2O-II < HSO4鈥?/sup>路NH4+-II with the respective 谓2-SOH at 736.7, 740.5, and 802.2 cm鈥? increasing in the same order. In HSO4鈥?/sup>路(H2O)n, coupling appeared when n was from 1 to 8. For HSO4鈥?/sup>路(D2O)n, no coupling between 谓2-SOH and D2O librations made it possible to understand the hydrogen bonding effect on the 谓2-SOH. The frequencies of 谓2-SOH for clusters HSO4鈥?/sup>(D2O)n almost linearly decreased from 752.0 to 854.6 cm鈥? with n from 1 to 10.