The Electronic Structure of Crystalline and Aqueous Solution of LiBr, NaBr, KBr, and KBrO3: in-situ Br L-edge NEXAFS Study

Authors

Shuji Matsuo, Fukuoka UniversityFollow
Ponnusamy Nachimuthu, University of Nevada, Las VegasFollow
Dennis W. Lindle, University of Nevada, Las VegasFollow
Hisanobu Wakita, Fukuoka UniversityFollow
Rupert C. Perera, Lawrence Berkeley National LaboratoryFollow

Document Type

Article

Publication Date

2003

Publication Title

Journal of Physical Chemistry B

Volume

107

Issue

46

First page number:

12562

Last page number:

12565

Abstract

The electronic structures of crystalline and aqueous solutions of LiBr, NaBr, KBr, and KBrO_³ were studied using in-situ Br L-edge near-edge X-ray absorption fine structure (NEXAFS) under ambient conditions. The direct observation of the ligand-field potential (10Dq) allows the determination of their dependence on the interatomic distances between Br and the first near neighbor in crystalline LiBr, NaBr, KBr, and KBrO_³ and the effect of hydration in the corresponding aqueous solutions. DV-Xa molecular-orbital calculations show that for both crystalline and aqueous solutions of KBr, the transitions occur from Br 2p to the unoccupied states containing mainly 4d orbitals of Br. The 5s and 5p orbitals of Br and 3d orbitals of K also contribute to the unoccupied states in addition to the 4d orbitals of neighbor Br due to the orbital mixing in crystalline KBr.

Keywords

Atomic orbitals; Bromides; Bromine compounds; Electron configuration; Electronic structure; X-ray Absorption Near Edge Structure

Disciplines

Analytical Chemistry | Atomic, Molecular and Optical Physics | Biological and Chemical Physics | Elementary Particles and Fields and String Theory | Physical Chemistry

Language

English

Permissions

Use Find in Your Library, contact the author, or use interlibrary loan to garner a copy of the article. Publisher copyright policy allows author to archive post-print (author’s final manuscript). When post-print is available or publisher policy changes, the article will be deposited

Repository Citation

Matsuo, S., Nachimuthu, P., Lindle, D. W., Wakita, H., Perera, R. C. (2003). The Electronic Structure of Crystalline and Aqueous Solution of LiBr, NaBr, KBr, and KBrO3: in-situ Br L-edge NEXAFS Study. Journal of Physical Chemistry B, 107(46), 12562-12565.