Halide鈥揘itrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations
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- 作者：Kim M. L. Lapere ; Marcus Kettner ; Peter D. Watson ; Allan J. McKinley ; Duncan A. Wild
- 刊名：Journal of Physical Chemistry A
- 出版年：2015
- 出版时间：September 17, 2015
- 年：2015
- 卷：119
- 期：37
- 页码：9722-9728
- 全文大小：341K
- ISSN：1520-5215
文摘
The gas phase anion photoelectron spectra are presented for the halide鈥搉itrogen clusters X鈥?/sup>路路路(N2)n, where X = Br and I and n 鈮?5. Electron binding energies for each cluster in the halide series are determined, with no evidence observed for first solvation shell closure in either series. High level ab initio calculations at the CCSD(T) level of theory are presented for the anion and neutral halogen鈥搉itrogen complexes. For the anion species, two minima are predicted corresponding to a loosely bound C2v 鈥淭-shaped鈥?species and to a higher energy covalently bound 鈥渢riangle鈥?C2v symmetry geometry. For the neutral species, three stationary points were located, two of which display similar form to the anion minima and a third which is linear, i.e., C鈭?i>v symmetry. The 鈥淭-shaped鈥?geometry is a transition state linking equivalent C鈭?i>v symmetry minima. Cluster dissociation energies (D0) were determined, for both anion and neutral global minima at the CCSD(T) complete basis set limit, to be 7.8 kJ mol鈥? and 7.0 kJ mol鈭? and 3.5 kJ mol鈭? and 5.0 kJ mol鈭? for the bromine and iodine species, respectively.