Abstract We study the dependence of aurophilic attraction (Au I –Au ) in perpendicular model systems type [(ClAuPH 3 2 ] on ab initio method, basis set and different pseudopotentials used, relativity. The effects varying „halogen”︁ (X = F, H, Cl, Me, Br, ‐C≡CH, I), „phosphine”︁ (L PH , PMe ‐N≡CH) metal (M Cu, Ag, Au) M–M′ interaction [(XML) dimer are also studied. depth potential increases with softness group X. It decreases by 27% for M Au, X Cl L if relativistic omitted at fixed geometry.

A new class of molecules, WAu12 (see picture) and its isoelectronic analogues, has been proposed theoretically studied. The calculated radial WAu distance is unusually short, 268 pm at the best level theory. frontier orbitals, both HOMO LUMO, have fivefold degenerate hg symmetry. gap between them approaches 3 eV. Possible applications these clusters are discussed.

The nature of the aurophilic interaction is studied by applying local second-order Mo/ller–Plesset perturbation theory (LMP2) on model dimers [X–Au–PH3]2 (X=H, Cl) type. possibility to decompose correlation contribution energy in dimer (A–B) into different excitation classes reveals that dispersion (A→A′,B→B′) accompanied an almost equally important ionic component (A→A′,B→A′), at shorter distances. Double excitations where least one electron originates from gold 5d orbitals account for 90%...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTQuasirelativistic Pseudopotential Study of Species Isoelectronic to Uranyl and the Equatorial Coordination UranylPekka Pyykkoe, Jian Li, Nino RunebergCite this: J. Phys. Chem. 1994, 98, 18, 4809–4813Publication Date (Print):May 1, 1994Publication History Published online1 May 2002Published inissue 1 1994https://pubs.acs.org/doi/10.1021/j100069a007https://doi.org/10.1021/j100069a007research-articleACS PublicationsRequest reuse permissionsArticle...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMatrix Infrared Spectroscopic and ab Initio Studies of ZnH2, CdH2, Related Metal Hydride SpeciesTim M. Greene, Wendy Brown, Lester Andrews, Anthony J. Downs, George V. Chertihin, Nino Runeberg, Pekka PyykkoCite this: Phys. Chem. 1995, 99, 20, 7925–7934Publication Date (Print):May 1, 1995Publication History Published online1 May 2002Published inissue 1...

Computational results up to the CCSD(T)/aug-cc-pV5Z level are presented as support for newly observed argon containing compound, hydrido argonfluoride (HArF). The molecule is calculated be linear with R(H–Ar)=132.9 pm and R(Ar–F)=196.9 pm. vibrational frequencies, corrected anharmonicity matrix effects, 462 (Ar–F stretch), 686 (bend) 1916 cm−1 (Ar–H stretch). These in good agreement corresponding experimentally frequencies of 435.7, 687.0, 1969.5 isolated species [Nature 406, 874 (2000)]....

Eine neue Klasse von Molekülen, WAu12 (siehe Bild) und seine isoelektronischen Analoga, wurde vorgeschlagen theoretisch untersucht. Der berechnete radiale W-Au-Abstand ist ungewöhnlich klein – 268 pm auf dem besten Theorieniveau. Beide Grenzorbitale (HOMO LUMO) haben die fünffach entartete hg-Symmetrie; Lücke zwischen ihnen beträgt 3 eV. Mögliche Anwendungen dieser Cluster werden vorgestellt.

We report an open-shell species containing xenon, HXeO ((2)Sigma), prepared by UV photolysis of H(2)O/Xe or N(2)O/HBr/Xe solid mixtures at 7 K and subsequent thermal mobilization oxygen atoms >/=30 K. The H-Xe stretching absorption in Xe is 1466.1 cm(-1), it shifts to 1070.3 cm(-1) upon deuteration. extensive ab initio calculations indicate that intrinsically stable, owing significant ionic covalent contributions its bonding. formation ((2)Sigma) radicals these experiments suggests...

Peroxyl radicals (RO

Counterpoise-corrected supermolecular calculations on the title molecules at MP2, CCSD, and CCSD(T) levels are used to extract a van der Waals radius of 224 pm for Rn, 6 more than Xe. The spin–orbit effects found significantly stabilize Rn2 RnXe. Van C6 C8 coefficients, which in good agreement with both experiment TDMP2 calculations, were obtained from large distances. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66: 131–140,

The reaction between thioether phosphine gold(I) precursors such as [AuCl(Ph2PCH2SPh)], 1, or [Au(Ph2PCH2SPh)2]CF3SO3 and PdCl2(NCPh)2 affords the new compounds [(AuCl(Ph2PCH2SPh)2PdCl2], 2, [AuPdCl2(Ph2PCH2SPh)2]CF3SO3, 3. crystal structure of complex 2 has sterically unhindered Pd(II) Au(I) at a distance 314 pm. Quasirelativistic pseudopotential calculations on [AuPdCl3(PH2CH2SH)(SH2)] models give short Au-Pd distances second-order Møller-Plesset (MP2) level long Hartree-Fock (HF) level. A...

The bonding strength of N-heterocyclic carbene (NHC) ligands to a neutral AuCl test moiety are compared that several phosphanes and other ligands. Of the studied, NHCs clearly form strongest bonds AuCl. A simplified triangular CN2 model is also introduced for NHCs.

High-yield synthesis of gold(I) thionato complexes, bis(pyridine-2-thionato)gold(I) chloride (1) and bis(pyridine-4-thionato)gold(I) (2), are described. According to their solid-state structures, a linear coordination Au(I), equiplanar the ligands two weak gamma-agostic interactions found in both these complexes despite different relative positions N S atoms pyridinethionato ligands. Density functional theory calculations on 1 2 reproduce observed X-ray structures. Even though C-H...Au Au(I)...

The complex [Ag(Py)3][Au(C6F5)2]·Py (1) (Py = pyridine) has been prepared by the reaction of NBu4[Au(C6F5)2] with AgClO4 in presence pyridine. crystallographic measurements indicate an extended unsupported one-dimensional chain alternating gold and silver atoms. This arrangement is due to formation molecular Au−Ag ion pairs, π-stacking C6F5 pyridine arene ligands packing effects that lead pairs at short distance. Theoretical calculations based on approximate experimental distances angles...

The experimental crystal structure of Tl2Pt(CN)4 suggests a molecular crystal. Theoretical calculations on the monomer give much shorter Tl−Pt distance 287.7 pm. correlation-induced s2−d8 interaction strongly shortens bond, but crystal-field effects are suggested to overcompensate for this contribution. UV bands well-reproduced.

Small flashes (b) occur during the freezing of triethylgallium samples in liquid nitrogen, and on warming from −196°C this is accompanied by decomposition (a). This effect was observed determination crystal structures GaMe3 GaEt3, which both show intermolecular interactions between their electron-deficient gallium atoms alkyl groups neighboring molecules.

Quantum chemical calculations of the nuclear shielding tensor, quadrupole coupling and spin-rotation tensor are reported for Xe dimer using ab initio quantum methods. The binary shift delta, anisotropy Delta sigma, component along internuclear axis chi( parallel ), constant C( perpendicular ) presented as a function distance. basis set superposition error is approximately corrected by counterpoise correction (CP) method. Electron correlation effects systematically studied via Hartree-Fock,...

Quasirelativistic pseudopotential ab initio calculations on tetrahedral (AuPH3)2+4 reproduce the experimental Au–Au distance in [AuP(But)3]2+4 and suggest that covalent correlation bonding this two-electron, four-centre system are comparable.