SUPPORTING INFORMATION (comparison to data about gas phase, free-standing,
Ag nanoclusters from the literature).
First of all, we applied our calculation methods for calculation of the absorption
(or excitation of luminescence) spectra of simplest Ag nanoclusters dispersed in the gas
phase, such as dimers, trimers and tetramers. The results of our calculations are listed in
the Table, where the experimental data from the previous literature is shown for
comparison with our calculation results. The distances between the Ag atoms comprising
the respective Ag nanoclusters have been optimized using DFT method with LCwPBE/Aug-cc-pVTZ-PP functional/basic set; and the optimized distances are post-signed
in Fig.S1 of this Section. In the particular case of the free-standing gas phase tetramer
Ag42+, which has a 3-dimensional structure, the optimized geometry was a tetrahedron, as
shown in Figure S1. Therefore, we applied our computing methods for calculation of
parameters of the gas phase Ag42+ nanoclusters in a tetrahedron shape; note a rhomb
shape for a Ag42+ nanocluster was argued above to occur when this tetramer was
dispersed in the lattice of the oxyfluoride glass host. Noteworthy, we have found the
rhomb structure for a free-standing gas phase Ag42+ nanocluster is not structurally stable.
Table. Energy of the lowest singlet excited state of free-standing (gas phase) Ag20 dimer,
Ag2+ dimer, Ag3+ trimer and Ag42+ tetramer. Experimental data are taken from the Ref.
[22]; theoretical data are taken from Refs. [16-21]. Our calculation data are shown in the
right column.
Ag cluster
Ag20
Ag2+
Data from literature
Theoretical
Experimental
work
data [22]
Refs. [16-21]
2.85
2.87
No data
3.15
This work calculation
LC-wPBE/
Aug-cc-pVTZCASPT2
PP
3.06
2.88
3.11
2.88
Ag3+
No data
4.11
4.10
3.98
Ag42+
No data
No data
4.91
4.91
Ag
Ag
2.66 Å
2.54 Å
Ag
2.72 Å
Ag
Ag
2.78 Å
Ag
2.66 Å
2.66 Å
Ag
Ag
Ag
Ag20
Ag2+
Ag
Ag
Ag3+
Figure S1. Geometries of Ag20, Ag2+, Ag3+ and Ag42+ which are optimized using DFT
method with LC-wPBE/Aug-cc-pVTZ-PP functional/basic set.
Ag42+