| Autor: |
Nhat PV; Department of Chemistry, Can Tho University, Can Tho, Vietnam.; Molecular and Materials Modeling Laboratory, Can Tho University, Can Tho, Vietnam., Si NT; Department of Chemistry, Can Tho University, Can Tho, Vietnam., Fielicke A; Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, Berlin, Germany., Kiselev VG; Novosibirsk State University, 1 Pirogova Str., 630090 Novosibirsk, Russia.; Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya Str., 630090 Novosibirsk, Russia., Nguyen MT; Institute for Computational Science and Technology (ICST), Ho Chi Minh City, Vietnam. tho.nm@icst.org.vn. |
| Abstrakt: |
The geometry of the neutral Au 18 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 17 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 18 isomers are close to each other, within ∼3 kcal mol -1 , 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 -1 , close to the most prominent experimental feature found at 78 cm -1 . 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 18 Kr 1,2 complexes. |
