Theory of the d¹⁰–d¹⁰ Closed‐Shell Attraction: 2. Long‐Distance Behaviour and Nonadditive Effects in Dimers and Trimers of Type [(x‐Au‐L)_n] (n = 2, 3; X = Cl, I, H; L = PH₃, PMe₃, ‐N≡CH)

Abstract

Abstract:We study the nature of the aurophilic attraction (Au'-Au') at its long-range limit for the model systems [(X-Au-L),] (n = 2, 3; X = C1, I, L = PH,, PMe,; X = H, L = -N-CH) at the ab initio M P 2 and Hartree-Fock levels. The nature of the interactions and nonadditive effects at various orientations are related to simple electrostatic induction and dispersion expressions involving the individual properties of each monomer.Keywords a b initio calculations * closed-shell attraction -gold * long-range interactions * relativistic effects

Aurophilicity: The Effect of the Neutral Ligand L on [{ClAuL}2] Systems

“…[19,20] These dispersion mechanisms were subsequently seen in detail by a local-orbital approach at MP2 and higher levels by Runeberg et al [21] and also in work on solid AgCl and AuCl by Doll et al [22] and on the [{XMPH 3 } 2 ] (X= H,Cl; M = Cu À Au) molecules by Magnko et al [23] at the MP2 and LMP2 levels. They correspond to the virtual charge transfer of type (A !…”

“…Trends associated with the ligands: For the [{XAuPH 3 } 2 ] model dimers [2,20,30] it was found that soft ligands, X, gave a stronger interaction. Later experimental evidence (see references [4,8]) points in the same direction.…”

“…For cubic, solid AgCl and AuCl, Doll et al [22] found the pairwise interactions to predominate. Molecular studies on [(XAuL) 3 ] trimers [20] or other systems [48] at the MP2 level, or of [(XMPH 3 ) 3 ] systems at the DFT (BP86) level [49] suggest small higher-order effects. The reservations are that the triple virtual excitations of the Axilrod-Teller-Muto interaction do not actually exist at the MP2 level, and that supramolecular DFT studies on metallophilicity are doubtful.…”

Vapor‐ and Mechanical‐Grinding‐Triggered Color and Luminescence Switches for Bis(σ‐fluorophenylacetylide) Platinum(II) Complexes

“…To precisely describe the molecular properties, one additional f-type polarization function was implemented for platinum(II) atom (a = 0.18). [57] To make a comparison between monomeric and dimeric models for 4·0.5 CH 2 Cl 2 , the DFT calculations were performed on both the monomer (Tables S11 and S12) and the dimer (Tables S4 and S5) having exactly the same geometry. Compared with a significant d z 2(Pt) orbital contribution to the HOMOs in the dimer (Table S4), the corresponding contribution from d z 2(Pt) orbital in the monomer (Table S11) is negligible.…”

Effects of Different Amount of Crystalline Solvate Molecules on Solid Structures and Photophysical Properties of a Platinum(II) Moiety with 4,4′‐Dibromo‐2,2′‐Bipyridine Ligand

“…To precisely describe the electronic structures, one additional f-type polarization function was implemented for the platinum(II) atom (α f = 0.18). [41,42] To compare transition characteristics that contribute to the absorption and emission spectra in crystalline species, TD-DFT calculations were performed on 1·1/3(CH 2 Cl 2 ) and 1·3/2(CH 2 Cl 2 ) using a pair of symmetry-related platinum(II) moieties. As the solvate molecules were found to exert an insignificant influence on the calculated results, all the calculations were performed by using a pair of symmetry-related square-planar platinum(II) moieties without considering the solvate molecules.…”