Test of Computational Approaches for Gold-Thiolate Clusters Calculation

Nadezhda N. Nikitina, Daria A. Pichugina, Alexander V. Oleynichenko, Oxana N. Ryzhova, Kirill E. Kopylov, Vladimir V. Krotov, Nikolay E. Kuz’menko


High-level procedures (MP2, CCSD, CCSD(T)) and reliable experimental data have been used to assess the performance of a variety of exchange-correlation functionals for the calculation of structures and energies of small models of thiolate-protected gold clusters. Clusters represent rather complicated objects for examination, therefore the simple models including Au2, AuS were considered to find an appropriate method to calculate Au-Au and Au-S interactions in protected clusters. The mean unsigned errors of the quantum chemical methods were evaluated via reliable experimental bond distances and dissociation energies of Au2 and AuS. Based on the calculation, the SVWN5, TPSS+D3, PBE96+D3, and PBE0+D3 were found to give the most reliable results and can be recommended for calculation of the structure and properties of thiolate-protected gold clusters. The influence of the relativistic corrections calculated in Dirac-Coulomb-Breit framework and inclusion of dispersion corrections on the structure and energy of thiolate-protected gold clusters have been analyzed.

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Polyakov, I.V., Moskovsky, A.A., Nemukhin, A.V.: Multi-Scale Supercomputing of Large Molecular Aggregates: A Case Study of the Light-Harvesting Photosynthetic Center. Supercomputing Frontiers and Innovations 2, 48–54 (2015), DOI: 10.14529/jsfi150403

Usher, W., Wald, I., Knoll, A., Papka, M., Pascucci, V.: In Situ Exploration of Particle Simulations with CPU Ray Tracing. Supercomputing Frontiers and Innovations 3, 4–18 (2016), DOI: 10.14529/jsfi160401

Liu, Y., Tian, Z., Cheng, L.: Size evolution and ligand effects on the structures and stability of (AuL)n (L = Cl, SH, SCH3, PH2, P(CH3)2, n = 113) clusters. RSC Advances. 6, 4705–4712 (2016), DOI: 10.1039/C5RA22741K

Bishea, G.A., Morse, M.D.: Spectroscopic studies of jetcooled AgAu and Au2. The Journal of Chemical Physics 95, 5646–5659 (1991), DOI: 10.1063/1.461639

Kokkin, D.L., Zhang, R., Steimle, T.C.: AuS Bonding Revealed from the Characterization of Diatomic Gold Sulfide, AuS. TheJournal of Physical Chemistry A A 119, 11659–11667 (2015), DOI: 10.1021/acs.jpca.5b08781

Dunning Jr.T.H.: Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. The Journal of Chemical Physics 90, 1007–1023 (1989), DOI: 10.1063/1.456153

Peterson, K.A., Puzzarini, C.: Systematically convergent basis sets for transition metals. II. Pseudopotential-based correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements. Theoretical Chemistry Accounts 114, 283–296 (2005), DOI: 10.1007/s00214-005-0681-9

Stevens, W.J., Krauss, M., Basch, H., Jasien, P.G.: Relativistic compact effective potentials and efficient, shared-exponent basis sets for the third-, fourth-, and fifth-row atoms. Canadian Journal of Chemistry 70, 612–630 (1992), DOI: 10.1139/v92-085

Hay, P.J., Wadt, W.R.: Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg. The Journal of Chemical Physics 82, 270–283 (1985), DOI: 10.1063/1.448799

Dyall, K.G.: An exact separation of the spinfree and spindependent terms of the Dirac- CoulombBreit Hamiltonian. The Journal of Chemical Physics 100, 2118–2127 (1994), DOI: 10.1063/1.466508

Laikov, D.: A new class of atomic basis functions for accurate electronic structure calculations of molecules. Chemical Physics Letters 416, 116–120 (2005), DOI: 10.1016/j.cplett.2005.09.046

Grimme, S., Antony, J., Ehrlich, S., Krieg H.: A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. The Journal of Chemical Physics 132, 154101(1–19) (2010), DOI: 10.1063/1.3382344

Valiev, M., Bylaska, E.J., Govind, N., Kowalski, K., Straatsma, T.P., Van Dam, H.J.J., Wang, D., Nieplocha, J., Apra, E., Windus, T.L., De Jong, W.A.: NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations. Computer Physics Communications 181, 1477–1489 (2010), DOI: 10.1016/j.cpc.2010.04.018

Laikov, D.N.: PRIRODA-04: a quantum-chemical program suite. New possibilities in the study of molecular systems with the application of parallel computing. Russian Chemical Bulletin, International Edition 54, 820–826 (2005), DOI: 10.1007/s11172-005-0329-x

Sadovnichy, V., Tikhonravov, A., Voevodin, Vl., Opanasenko, V.: Lomonosov: Supercomputing at Moscow State University. In Contemporary High Performance Computing: From Petascale toward Exascale (Chapman & Hall/CRC Computational Science), Boca Raton, USA, CRC Press. 283–307 (2013)

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