质子化分子团簇阳离子（(NH3)n+，n = 2 - 4以及(CH3OH)n+，n = 2,3）的红外预解离光谱

Infrared predissociation spectroscopy of cluster cations of protic molecules, (NH3)n+, n=2-4 and (CH3OH)n+, n=2,3.

作者信息

Hachiya Masaki, Matsuda Yoshiyuki, Suhara Ken-Ichiro, Mikami Naohiko, Fujii Asuka

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki-Aoba, Aoba-ku, Sendai 980-8578, Japan.

出版信息

J Chem Phys. 2008 Sep 7;129(9):094306. doi: 10.1063/1.2971186.

DOI:10.1063/1.2971186

PMID:19044869

Abstract

Infrared predissociation spectroscopy is carried out for the structure investigation of unprotonated cluster cations of protic molecules such as ammonia and methanol, which are generated through vacuum-ultraviolet one-photon ionization of their jet-cooled neutral clusters. The observed spectral features show that the cluster cations have the proton-transferred type structures, where a pair of a protonated cation and a neutral radical, NH(4) (+)...NH(2) or CH(3)OH(2) (+)...OCH(3), is formed. Theoretical calculations at the MP2 and B3LYP levels support the formation of the proton-transferred type structures for the cluster cations, and indicate that they are formed by proton-transfer following the photoionization of the neutral clusters.

摘要

对质子化分子（如氨和甲醇）的未质子化簇阳离子进行红外预解离光谱研究，这些阳离子是通过对其喷射冷却的中性簇进行真空紫外单光子电离产生的。观察到的光谱特征表明，簇阳离子具有质子转移型结构，其中形成了一对质子化阳离子和中性自由基，即NH(4) (+)...NH(2) 或CH(3)OH(2) (+)...OCH(3)。在MP2和B3LYP水平上的理论计算支持簇阳离子形成质子转移型结构，并表明它们是在中性簇光致电离后通过质子转移形成的。