A photoelectron spectroscopy and ab initio study of the structures and chemical bonding of the B25- cluster

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Author(s)

  • Zachary A. Piazza
  • Ivan A. Popov
  • Wei-Li Li
  • Rhitankar Pal
  • Alexander I. Boldyrev
  • Lai-Sheng Wang

Detail(s)

Original languageEnglish
Article number034303
Journal / PublicationJournal of Chemical Physics
Volume141
Issue number3
Publication statusPublished - 21 Jul 2014
Externally publishedYes

Abstract

Photoelectron spectroscopy and ab initio calculations are used to investigate the structures and chemical bonding of the B25 - cluster. Global minimum searches reveal a dense potential energy landscape with 13 quasi-planar structures within 10 kcal/mol at the CCSD(T)/6-311+G(d) level of theory. Three quasi-planar isomers (I, II, and III) are lowest in energy and nearly degenerate at the CCSD(T) level of theory, with II and III being 0.8 and 0.9 kcal/mol higher, respectively, whereas at two density functional levels of theory isomer III is the lowest in energy (8.4 kcal/mol more stable than I at PBE0/6-311+G(2df) level). Comparison with experimental photoelectron spectroscopic data shows isomer II to be the major contributor while isomers I and III cannot be ruled out as minor contributors to the observed spectrum. Theoretical analyses reveal similar chemical bonding in I and II, both involving peripheral 2c-2e B-B σ-bonding and delocalized interior σ- and π-bonding. Isomer III has an interesting elongated ribbon-like structure with a π-bonding pattern analogous to those of dibenzopentalene. The high density of low-lying isomers indicates the complexity of the medium-sized boron clusters; the method dependency of predicting relative energies of the low-lying structures for B25- suggests the importance of comparison with experiment in determining the global minima of boron clusters at this size range. The appearance of many low-lying quasi-planar structures containing a hexagonal hole in B25 - suggests the importance of this structural feature in maintaining planarity of larger boron clusters. © 2014 AIP Publishing LLC.

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Citation Format(s)

A photoelectron spectroscopy and ab initio study of the structures and chemical bonding of the B25- cluster. / Piazza, Zachary A.; Popov, Ivan A.; Li, Wei-Li et al.
In: Journal of Chemical Physics, Vol. 141, No. 3, 034303, 21.07.2014.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review