Supporting information for the JPC-C paper entitled:
“Influence of Silver Doping on the Photoluminescence of Protected AgnAu25−n Nanoclusters: A TD-DFT Investigation” Francesco Muniz-Miranda,∗ Maria Cristina Menziani, and Alfonso Pedone∗ University of Modena and Reggio Emilia (UniMoRE), Department of Chemical and Geological Sciences (DSCG), Via G. Campi 183, I-41125, Modena, Italy E-mail:
[email protected];
[email protected]
∗
To whom correspondence should be addressed
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As reported in the main paper, we have carried out structural relaxations on the metal atoms of the Agn Au2+ 25−n (a, b) family (n=13,12,11,10,9), followed by harmonic normal modes calculations. We found no imaginary frequency, thus the relaxed structures are true geometries of minimal energy. In Figure S1 is reported the IR spectra of the Agn Au2+ 25−n (a) family. As can be seen, the
Fig. S1: IR spectra of the cores of Agn Au2+ 25−n (a) clusters, with n=(13,12,11,10,9). The numbers represent the five normal modes giving the most intense contribution to the spectrum. These numbered normal modes are shown in subsequent Figure S2.
spanned range of frequencies contracts when Ag doping is smaller (i.e. Au content is higher). Moreover, the maximum frequency fall from ∼231 cm−1 to 217 cm−1 , which is expected since 2
we have, in the harmonic approximation s ω=
k µ
,
and the mass of the Au atom is almost double of that of the Ag atom. The 5 most intense normal modes for each stoichiometry are reported in Figure S2. The normal modes of n=13,12 are largely the same, both in frequency and in displacements. The same could be said of n=11,10, with just normal modes #72 and #71 that switch their intensity. The distribution of normal modes of n=9 is rather different from those of others. That said, some normal modes are recurrent between all these stoichiometries. In particular: • normal mode #72 of n=13,12 corresponds to normal mode #73 of n=11,10 and to normal mode #74 of n=9; • normal mode #73 of n=13,12 corresponds to normal mode #74 of n=11,10 and to normal mode #75 of n=9; • normal mode #74 of n=13,12 corresponds to normal mode #75 of n=11,10; • normal mode #68 of n=13,12 seems very similar to normal mode #69 of n=11 and to normal mode #71 of n=9.
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Fig. S2: Normal modes of the cores of Agn Au2+ 25−n (a) clusters, with n=(13,12,11,10,9). Hydrogen atoms have been omitted for clarity.
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