The charge state of pt in binary compounds and synthetic minerals determined by x-ray absorption spectroscopy and quantum chemical calculations

Abstract

The binary synthetic compounds of Pt with chalcogens (O, S, Se, Te), pnictogens (As, Sb, Bi), and intermetallic compounds with Ga, In, and Sn of various stoichiometry were studied via X-ray absorption spectroscopy (XAS). The partial atomic charges of Pt in the compounds were computed using quantum chemical density functional theory (DFT) based methods: the Bader (QTAIM) method, and the density-derived electrostatic and chemical (DDEC6) approach. Strong positive correlations were established between the calculated partial atomic charges of Pt and the electronegativity (χ) of ligands. The partial charge of Pt in PtL2 compounds increases much sharply when the ligand electronegativity increases than the Pt partial charge in PtL compounds. The effect of the ligand-to-Pt atomic ratio on the calculated Pt partial charge depended on ligand electronegativity. The DDEC6 charge of Pt increases sharply with the growth of the number of ligands in PtSn (n = 1, 2; electronegativity χ(S) >> χ(Pt)), weakly depends on the phase composition in PtTen (n = 1, 2; χ(Te) is slightly lower than χ(Pt)), and decreases (becomes more negative) with increase of the ligand-to-Pt ratio in intermetallic compounds with electron donors (χ(L) < χ(Pt), L = Ga, In, Sn). According to XANES spectroscopy, the number of 5d (L2,3 absorption edges) and 6p (L1-edge) electrons at the Pt site decreased when ligand electronegativity increased in chalcogenides and pnictides groups. An increase of the ligand-to-Pt ratio resulted in the increase of the Pt L3-edge white line intensity and area in all studied compounds. In the case of chalcogenides and pnictides, this behavior was consistent with the electronegativity rule as it indicated a loss of Pt 5d electrons caused by the increase of the number of ligands, i.e., acceptors of electrons. However, in the case of ligands–electron donors (Te, Sn, Ga, In) this observation is in apparent contradiction with the electronegativity arguments as it indicates the increase of the number of Pt 5d-shell vacancies (holes) with the increase of the number of the ligands, for which the opposite trend is expected. This behavior can be explained in the framework of the charge compensation model. The loss of the Pt d-electrons in compounds with low ligand electronegativity (χ(Pt) > χ(L)) was overcompensated by the gain of the hybridized s-p electron density, which was confirmed by Pt L1-edge spectra analysis. As a result, the total electron density at the Pt site followed the electronegativity rule, i.e., it increased with the growth of the number of the ligands-electron donors. The empirical correlations between the Pt partial atomic charges and parameters of XANES spectral features were used to identify the state of Pt in pyrite, and can be applied to determine the state of Pt in other ore minerals.