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Title: A photoelectron spectroscopy and ab initio study of B21-: Negatively charged boron clusters continue to be planar at 21

Abstract

The structures and chemical bonding of the B21- cluster have been investigated by a combined photoelectron spectroscopy and ab initio study. The photoelectron spectrum at 193 nm revealed a very high adiabatic electron binding energy of 4.38 eV for B21- and a congested spectral pattern. Extensive global minimum searches were conducted using two different methods, followed by high-level calculations of the low-lying isomers. The global minimum of B21- was found to be a quasiplanar structure with the next low-lying planar isomer only 1.9 kcal/mol higher in energy at the CCSD(T)/6-311-G* level of theory. The calculated vertical detachment energies for the two isomers were found to be in good agreement with the experimental spectrum, suggesting that they were both present experimentally and contributed to the observed spectrum. Chemical bonding analyses showed that both isomers consist of a 14-atom periphery, which is bonded by classical two-center two-electron bonds, and seven interior atoms in the planar structures. A localized two-center two-electron bond is found in the interior of the two planar isomers, in addition to delocalized multi-center σ and π bonds. The structures and the delocalized bonding of the two lowest lying isomers of B21- were found to be similar to those inmore » the two lowest energy isomers in B19-.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1097960
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 136; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

Piazza, Zachary A., Li, Wei-Li, Romanescu, Constantin, Sergeeva, Alina P., Wang, Lai-Sheng, and Boldyrev, Alexander I. A photoelectron spectroscopy and ab initio study of B21-: Negatively charged boron clusters continue to be planar at 21. United States: N. p., 2012. Web. doi:10.1063/1.3692967.
Piazza, Zachary A., Li, Wei-Li, Romanescu, Constantin, Sergeeva, Alina P., Wang, Lai-Sheng, & Boldyrev, Alexander I. A photoelectron spectroscopy and ab initio study of B21-: Negatively charged boron clusters continue to be planar at 21. United States. https://doi.org/10.1063/1.3692967
Piazza, Zachary A., Li, Wei-Li, Romanescu, Constantin, Sergeeva, Alina P., Wang, Lai-Sheng, and Boldyrev, Alexander I. 2012. "A photoelectron spectroscopy and ab initio study of B21-: Negatively charged boron clusters continue to be planar at 21". United States. https://doi.org/10.1063/1.3692967.
@article{osti_1097960,
title = {A photoelectron spectroscopy and ab initio study of B21-: Negatively charged boron clusters continue to be planar at 21},
author = {Piazza, Zachary A. and Li, Wei-Li and Romanescu, Constantin and Sergeeva, Alina P. and Wang, Lai-Sheng and Boldyrev, Alexander I.},
abstractNote = {The structures and chemical bonding of the B21- cluster have been investigated by a combined photoelectron spectroscopy and ab initio study. The photoelectron spectrum at 193 nm revealed a very high adiabatic electron binding energy of 4.38 eV for B21- and a congested spectral pattern. Extensive global minimum searches were conducted using two different methods, followed by high-level calculations of the low-lying isomers. The global minimum of B21- was found to be a quasiplanar structure with the next low-lying planar isomer only 1.9 kcal/mol higher in energy at the CCSD(T)/6-311-G* level of theory. The calculated vertical detachment energies for the two isomers were found to be in good agreement with the experimental spectrum, suggesting that they were both present experimentally and contributed to the observed spectrum. Chemical bonding analyses showed that both isomers consist of a 14-atom periphery, which is bonded by classical two-center two-electron bonds, and seven interior atoms in the planar structures. A localized two-center two-electron bond is found in the interior of the two planar isomers, in addition to delocalized multi-center σ and π bonds. The structures and the delocalized bonding of the two lowest lying isomers of B21- were found to be similar to those in the two lowest energy isomers in B19-.},
doi = {10.1063/1.3692967},
url = {https://www.osti.gov/biblio/1097960}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 136,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2012},
month = {Sun Jan 01 00:00:00 EST 2012}
}