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Title: Making sense of the conflicting magic numbers in WSi{sub n} clusters

Abstract

First principles studies on the geometric structure, stability, and electronic structure of WSi{sub n} clusters, n = 6-16, have been carried out to show that the observed differing “magic sizes” for WSi{sub n} clusters are associated with the nature of the growth processes. The WSi{sub 12} cluster, observed as a magic species in experiments reacting transition metal ions with silane, is not stable due to a filled shell of 18 electrons, as previously proposed, but due to its atomic structure that arrests further growth because of an endohedral transition metal site. In fact, it is found that all of these clusters, n = 6-16, have filled 5d shells except for WSi{sub 12}, which has a 5d{sup 8} configuration that is caused by crystal field splitting. The stability of WSi{sub 15}{sup +}, observed as highly stable in clusters generated by vaporizing silicon and metal carbonyls, is shown to be associated with a combination of geometric and electronic features. The findings are compared with previous results on CrSi{sub n} clusters.

Authors:
; ;  [1]
  1. Department of Physics, Virginia Commonwealth University, 701 West Grace Street, Richmond, Virginia 23220 (United States)
Publication Date:
OSTI Identifier:
22493548
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 7; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYLS; CHROMIUM SILICIDES; COMPARATIVE EVALUATIONS; CRYSTAL FIELD; ELECTRONIC STRUCTURE; ELECTRONS; MOLECULAR CLUSTERS; PHASE STABILITY; SILANES; SILICON; TUNGSTEN SILICIDES

Citation Formats

Abreu, Marissa Baddick, Reber, Arthur C., and Khanna, Shiv N. Making sense of the conflicting magic numbers in WSi{sub n} clusters. United States: N. p., 2015. Web. doi:10.1063/1.4928755.
Abreu, Marissa Baddick, Reber, Arthur C., & Khanna, Shiv N. Making sense of the conflicting magic numbers in WSi{sub n} clusters. United States. https://doi.org/10.1063/1.4928755
Abreu, Marissa Baddick, Reber, Arthur C., and Khanna, Shiv N. 2015. "Making sense of the conflicting magic numbers in WSi{sub n} clusters". United States. https://doi.org/10.1063/1.4928755.
@article{osti_22493548,
title = {Making sense of the conflicting magic numbers in WSi{sub n} clusters},
author = {Abreu, Marissa Baddick and Reber, Arthur C. and Khanna, Shiv N.},
abstractNote = {First principles studies on the geometric structure, stability, and electronic structure of WSi{sub n} clusters, n = 6-16, have been carried out to show that the observed differing “magic sizes” for WSi{sub n} clusters are associated with the nature of the growth processes. The WSi{sub 12} cluster, observed as a magic species in experiments reacting transition metal ions with silane, is not stable due to a filled shell of 18 electrons, as previously proposed, but due to its atomic structure that arrests further growth because of an endohedral transition metal site. In fact, it is found that all of these clusters, n = 6-16, have filled 5d shells except for WSi{sub 12}, which has a 5d{sup 8} configuration that is caused by crystal field splitting. The stability of WSi{sub 15}{sup +}, observed as highly stable in clusters generated by vaporizing silicon and metal carbonyls, is shown to be associated with a combination of geometric and electronic features. The findings are compared with previous results on CrSi{sub n} clusters.},
doi = {10.1063/1.4928755},
url = {https://www.osti.gov/biblio/22493548}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 7,
volume = 143,
place = {United States},
year = {Fri Aug 21 00:00:00 EDT 2015},
month = {Fri Aug 21 00:00:00 EDT 2015}
}