Hydrogen-bonded ring closing and opening of protonated methanol clusters H+(CH3OH)n (n = 4-8) with the inert gas tagging
Hydrogen-bonded ring closing and opening of protonated methanol clusters H+(CH3OH)n (n = 4-8) with the inert gas tagging
复制标题
惰性气体标记的质子化甲醇簇 H (CH3OH)n (n = 4-8) 的氢键闭环和开环
DOI：
10.1039/c5cp03379a
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Jer-Lai
中科院分区：
文献类型：
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作者：
Li;Ying-Cheng Hamashima;Toru Yamazaki;Ryoko Kobayashi;Tomohiro Suzuki;Yuta Mizuse;Kenta Fujii;Asuka Kuo;Jer-Lai
结合密度泛函理论计算，采用尺寸选择红外光谱技术研究了质子化甲醇簇H+(MeOH)n在n = 4-8范围内的优先氢键结构。将裸团簇的红外光谱与惰性气体Ar、Ne和N2标记的红外光谱进行比较，发现n≥5的团簇在标记后异构体分布发生了显著变化。用量子调和叠加法计算了簇的同分异构体分布与温度的关系。标记后簇温的下降很好地解释了随标记所观察到的光谱变化，这使得同分异构体的分布从开放和柔性的氢键网络类型转移到封闭和刚性的氢键网络类型。最近在质子化水团簇中发现了带有标记的异常异构体分布，在H+(MeOH)5中也发现了异常异构体分布。通过对载气依赖性的实验，探讨了异常的成因。
The preferential hydrogen bond (H-bond) structures of protonated methanol clusters, H+(MeOH)n, in the size range of n = 4–8, were studied by size-selective infrared (IR) spectroscopy in conjunction with density functional theory calculations. The IR spectra of bare clusters were compared with those with the inert gas tagging by Ar, Ne, and N2, and remarkable changes in the isomer distribution with the tagging were found for clusters with n ≥ 5. The temperature dependence of the isomer distribution of the clusters was calculated by the quantum harmonic superposition approach. The observed spectral changes with the tagging were well interpreted by the fall of the cluster temperature with the tagging, which causes the transfer of the isomer distribution from the open and flexible H-bond network types to the closed and rigid ones. Anomalous isomer distribution with the tagging, which has been recently found for protonated water clusters, was also found for H+(MeOH)5. The origin of the anomaly was examined by the experiments on its carrier gas dependence.