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A new look at the structure of the neutral Au18 cluster: hollow versus filled golden cage.
- Source :
- Physical Chemistry Chemical Physics (PCCP); 4/7/2023, Vol. 25 Issue 13, p9036-9042, 7p
- Publication Year :
- 2023
-
Abstract
- The geometry of the neutral Au<subscript>18</subscript> gold cluster was probed by a combination of quantum chemical calculations and far-infrared multiple photon dissociation (FIR-MPD) spectroscopy of a Kr messenger complex. Two low-lying isomers are identified to potentially contribute to the experimental IR spectrum, both being derived from a star-like Au<subscript>17</subscript> structure upon capping with one extra Au atom either inside (18_1) or outside (18_5) the star. In particular, the present detection of structure 18_1 by DFT computations where a golden cage encapsulates an endohedral Au atom, is intriguing as a stable core–shell isomer has, to our knowledge, never been found before for such small neutral gold clusters. DFT and local coupled-cluster (DLPNO and PNO-CCSD(T)) computations indicate that both Au<subscript>18</subscript> isomers are close to each other, within ∼3 kcal mol<superscript>−1</superscript>, on the energy scale. Although the exact energy ordering is again method-dependent and remains, at present, inconclusive, the most striking spectral signatures of both isomers are related to vibrational modes localized at atoms capping the inner pentaprism sub-structure that result in prominent peaks centered at ∼80 cm<superscript>−1</superscript>, close to the most prominent experimental feature found at 78 cm<superscript>−1</superscript>. The calculated IR spectra of both core–shell and hollow isomers are very similar to each other and both agree comparably well with the experimental FIR-MPD spectra of the Au<subscript>18</subscript>Kr<subscript>1,2</subscript> complexes. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14639076
- Volume :
- 25
- Issue :
- 13
- Database :
- Complementary Index
- Journal :
- Physical Chemistry Chemical Physics (PCCP)
- Publication Type :
- Academic Journal
- Accession number :
- 162755392
- Full Text :
- https://doi.org/10.1039/d2cp05422a