Experimental and theoretical 2p core-level spectra of size-selected gas-phase aluminum and silicon cluster cations : Chemical shifts, geometric structure, and coordination-dependent screening
(2019) In Physical Chemistry Chemical Physics 21(12). p.6651-6661- Abstract
We present 2p core-level spectra of size-selected aluminum and silicon cluster cations from soft X-ray photoionization efficiency curves and density functional theory. The experimental and theoretical results are in very good quantitative agreement and allow for geometric structure determination. New ground state geometries for Al
12
+
, Si
15
... (More)
(Less)
We present 2p core-level spectra of size-selected aluminum and silicon cluster cations from soft X-ray photoionization efficiency curves and density functional theory. The experimental and theoretical results are in very good quantitative agreement and allow for geometric structure determination. New ground state geometries for Al
12
+
, Si
15
+
, Si
16
+
, and Si
19
+
are proposed on this basis. The chemical shifts of the 2p electron binding energies reveal a substantial difference for aluminum and silicon clusters: while in aluminum the 2p electron binding energy decreases with increasing coordination number, no such correlation was observed for silicon. The 2p binding energy shifts in clusters of both elements differ strongly from those of the corresponding bulk matter. For aluminum clusters, the core-level shifts between outer shell atoms and the encapsulated atom are of opposite sign and one order of magnitude larger than the corresponding core-level shift between surface and bulk atoms in the solid. For silicon clusters, the core-level shifts are of the same order of magnitude in clusters and in bulk silicon but no obvious correlation of chemical shift and bond length, as present for reconstructed silicon surfaces, are observed.
- author
- organization
- publishing date
- 2019
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Physical Chemistry Chemical Physics
- volume
- 21
- issue
- 12
- pages
- 11 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- scopus:85063278454
- pmid:30855620
- ISSN
- 1463-9076
- DOI
- 10.1039/c8cp07169a
- language
- English
- LU publication?
- yes
- id
- b23aef6b-56c3-42ff-b994-0e60fce4e42b
- date added to LUP
- 2019-04-05 13:34:11
- date last changed
- 2024-06-11 07:50:16
@article{b23aef6b-56c3-42ff-b994-0e60fce4e42b,
abstract = {{<p><br>
We present 2p core-level spectra of size-selected aluminum and silicon cluster cations from soft X-ray photoionization efficiency curves and density functional theory. The experimental and theoretical results are in very good quantitative agreement and allow for geometric structure determination. New ground state geometries for Al <br>
<sub>12</sub><br>
<br>
<sup>+</sup><br>
, Si <br>
<sub>15</sub><br>
<br>
<sup>+</sup><br>
, Si <br>
<sub>16</sub><br>
<br>
<sup>+</sup><br>
, and Si <br>
<sub>19</sub><br>
<br>
<sup>+</sup><br>
are proposed on this basis. The chemical shifts of the 2p electron binding energies reveal a substantial difference for aluminum and silicon clusters: while in aluminum the 2p electron binding energy decreases with increasing coordination number, no such correlation was observed for silicon. The 2p binding energy shifts in clusters of both elements differ strongly from those of the corresponding bulk matter. For aluminum clusters, the core-level shifts between outer shell atoms and the encapsulated atom are of opposite sign and one order of magnitude larger than the corresponding core-level shift between surface and bulk atoms in the solid. For silicon clusters, the core-level shifts are of the same order of magnitude in clusters and in bulk silicon but no obvious correlation of chemical shift and bond length, as present for reconstructed silicon surfaces, are observed. <br>
</p>}},
author = {{Walter, Michael and Vogel, Marlene and Zamudio-Bayer, Vicente and Lindblad, Rebecka and Reichenbach, Thomas and Hirsch, Konstantin and Langenberg, Andreas and Rittmann, Jochen and Kulesza, Alexander and Mitrić, Roland and Moseler, Michael and Möller, Thomas and Von Issendorff, Bernd and Lau, J. Tobias}},
issn = {{1463-9076}},
language = {{eng}},
number = {{12}},
pages = {{6651--6661}},
publisher = {{Royal Society of Chemistry}},
series = {{Physical Chemistry Chemical Physics}},
title = {{Experimental and theoretical 2p core-level spectra of size-selected gas-phase aluminum and silicon cluster cations : Chemical shifts, geometric structure, and coordination-dependent screening}},
url = {{http://dx.doi.org/10.1039/c8cp07169a}},
doi = {{10.1039/c8cp07169a}},
volume = {{21}},
year = {{2019}},
}