The detailed structures of most of ligand-stabilized metal nanoclusters (NCs) remain unknown due to the absence of crystal structure data for them. In such a situation, quantum-chemical modeling is of particular interest. We compared the performance of different theoretical methods of geometry optimization and absorption spectra calculation for silver-thiolate complexes. We showed that the absorption spectra calculated with the ADC(2) method were consistent with the spectra obtained with CC2 method. Three DFT functionals (B3LYP, CAM-B3LYP, and M06-2X) failed to reproduce the CC2 absorption spectra of the silver-thiolate complexes.
K E Y W O R D SADC(2), CAM-B3LYP, CC2, M062X, silver nanoclusters, silver-thiolate complexes, TDDFT
| INTRODUCTIONLigand protected metal nanoclusters (NCs) have gained much attention in the last decade due to their unique physicochemical properties. These metal NCs typically measure less than 2 nm. [1,2] Electronic, chemical, and optical properties of NCs differ from both bulk and atomic scale materials. Optically active NCs may possess strong visible or near infrared luminescence, [3] which can be used in various applications, such as bioimaging, biosensing, and optical detection of biomolecules. [4] Among the great variety of NCs, gold (Au) NCs are the most extensively investigated due to their chemical stability. [5] However, fluorescent silver (Ag) clusters are the brightest, exhibiting high quantum yield and large absorption cross-section. [6] Various techniques have been developed for the synthesis of stable, water-soluble silver NCs by using dendrimers, [7] polymers, [8] polypeptides, [9,10] thiols, [11] DNA, [12,13] thiolated DNA, [14] and other ligands to stabilize silver ions. [15] The influence of various thiolates on binding energy with silver NCs has been studied in details. [16] The nature of the ligand seems to have a strong effect on fluorescent properties of noble metal NCs. [17] Noble metal NCs protected with thiolate ligands have been of interest because of their long-term stability, which allows one to use them as building blocks constructing assembled systems with novel and improved functions. [2] Silver-thiolate and silver-amino acid complexes are studied in many laboratories nowadays both theoretically and experimentally. [18][19][20] It is assumed that silver nanoclusters are stabilized by cysteine residues in protein matrices. [21,22] While the composition of the ligand-protected NCs can be analyzed using mass-spectroscopy technique, [23] their detailed structures remain unknown in many cases. In this respect, quantum-chemical modeling of silver-ligand complexes is of particular interest. [24][25][26][27][28][29][30][31][32] Gell and coworkers investigated thiolate-protected silver NCs that contained zero, two, or four confined electrons in the cluster core. [33] They found that the number of confined electrons determine the spectroscopic patterns. For systems with two or four confined electrons, strong absorption and fluorescence in the visible or even IR energ...