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Assessment of the basis set effect on the structural and electronic properties of organic-protected gold nanoclusters

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Abstract

We have investigated the structural and optical properties of five monolayer-protected gold nanoclusters with a combination of exchange–correlation functionals, namely B-PBE for the geometry relaxation and CAM-B3LYP for the time-dependent calculations. We have tested the accuracy of five different basis sets in reproducing the experimental structures of these nanoclusters, and we have found that even a rather small basis set (single zeta) can outperform a significantly larger one (double zeta) if some selected atoms are treated with polarization functions. Namely, the sulfur and phosphorous atoms of the capping thiols and phosphines usually are hypervalent when bonded to the gold inner core; therefore, polarization functions allow them significantly more structural flexibility. With the two best performing basis sets, we carried out optical calculations and found that the resulting UV–Vis profiles are largely similar, in particular the energy and orbital contributions of the optical gaps are very close. The results support the use of the small basis set proposed here to investigate larger nanoclusters with general hybrid and range-corrected hybrid functionals.

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Acknowledgments

This work and F.M.–M.’s postdoctoral fellowship at UniMoRE were supported by the Italian “Ministero dell’Istruzione, dell’Università e della Ricerca” (MIUR) through the “Futuro in Ricerca” (FIRB) Grant RBFR1248UI_002 entitled “Novel Multiscale Theoretical/Computational Strategies for the Design of Photo and Thermo responsive Hybrid Organic–Inorganic Components for Nanoelectronic Circuits,” and the “Programma di ricerca di rilevante interesse nazionale” (PRIN) Grant 2010C4R8M8 entitled “Nanoscale functional Organization of (bio)Molecules and Hybrids for targeted Application in Sensing, Medicine and Biotechnology” is also acknowledged. CINECA granted computation time within the research project AUNANMR-HP10CJ027S.

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Authors and Affiliations

  1. Department of Chemical and Geological Sciences (DSCG), University of Modena and Reggio Emilia (UniMoRE), Via G. Campi 103, 41125, Modena, Italy

    Francesco Muniz-Miranda, Maria Cristina Menziani & Alfonso Pedone

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  1. Francesco Muniz-Miranda
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  2. Maria Cristina Menziani
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  3. Alfonso Pedone
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Correspondence to Francesco Muniz-Miranda.

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Published as part of the special collection of articles “Charge Transfer Modeling in Chemistry”.

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Muniz-Miranda, F., Menziani, M.C. & Pedone, A. Assessment of the basis set effect on the structural and electronic properties of organic-protected gold nanoclusters. Theor Chem Acc 135, 94 (2016). https://doi.org/10.1007/s00214-016-1856-2

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