Microscopic solvation of NaBO2 in water: anion photoelectron spectroscopy and ab initio calculations

Yuan Feng; Min Cheng; Xiang-Yu Kong; Hong-Guang Xu; Wei-Jun Zheng

doi:10.1039/c1cp20831d

Microscopic solvation of NaBO2 in water: anion photoelectron spectroscopy and ab initio calculations

Phys Chem Chem Phys. 2011 Sep 21;13(35):15865-72. doi: 10.1039/c1cp20831d. Epub 2011 Aug 3.

Authors

Yuan Feng¹, Min Cheng, Xiang-Yu Kong, Hong-Guang Xu, Wei-Jun Zheng

Affiliation

¹ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

PMID: 21814667
DOI: 10.1039/c1cp20831d

Abstract

We investigated the microscopic solvation of NaBO(2) in water by conducting photoelectron spectroscopy and ab initio studies on NaBO(2)(-)(H(2)O)(n) (n = 0-4) clusters. The vertical detachment energy (VDE) of NaBO(2)(-) is estimated to be 1.00 ± 0.08 eV. The photoelectron spectra of NaBO(2)(-)(H(2)O)(1) and NaBO(2)(-)(H(2)O)(2) are similar to that of bare NaBO(2)(-), except that their VDEs shift to higher electron binding energies (EBE). For the spectra of NaBO(2)(-)(H(2)O)(3) and NaBO(2)(-)(H(2)O)(4), a low EBE feature appears dramatically in addition to the features observed in the spectra of NaBO(2)(-)(H(2)O)(0-2). Our study shows that the water molecules mainly interact with the BO(2)(-) unit in NaBO(2)(-)(H(2)O)(1) and NaBO(2)(-)(H(2)O)(2) clusters to form Na-BO(2)(-)(H(2)O)(n) type structures, while in NaBO(2)(-)(H(2)O)(3) and NaBO(2)(-)(H(2)O)(4) clusters, the water molecules can interact strongly with the Na atom, therefore, the Na-BO(2)(-)(H(2)O)(n) and Na(H(2)O)(n)···BO(2)(-) types of structures coexist. That can be seen as an initial step of the transition from a contact ion pair (CIP) structure to a solvent-separated ion pair (SSIP) structure for the dissolution of NaBO(2).