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Peter Schwerdtfeger

Publications and source records attributed to Peter Schwerdtfeger.

25 records · Page 2Linked to original sources
PubMed2003

Stability of the gold(i)-phosphine bond. A comparison with other group 11 elements.

The stability of gold phosphine complexes of the form [Au(PH(3))(n)()](+) (n = 1-4) and [AuCl(PH(3))(n)()] (n = 1-3) is analyzed in detail by applying quantum theoretical methods and compared to the coordination behavior of the lighter group 11 elements copper and silver. It is shown that, once [M(PH(3))(2)](+) or [MClPH(3)] (M = Cu, Ag, and Au) is formed, further coordination by PH(3) ligands is relatively weak; i.e., the energy gain to form [M(PH(3))(3)](+) from [M(PH(3))(2)](+) is less than 60 kJ mol(-)(1), and less than 100 kJ mol(-)(1) to form [MCl(PH(3))(2)] from [MClPH(3)]. Relativistic effects in gold significantly influence these factors and reduce the tendency for phosphine coordination beyond two-coordination. This implies that the most favored coordination number for gold is two with either a linear P-Au-P or P-Au-X arrangement (X = a strongly coordinating ligand like Cl(-)). Instead, X-Au-PH(3) units prefer to interact via close Au-Au contacts (aurophilic interactions) keeping the linear structure approximately intact, while the corresponding copper and silver compounds prefer PH(3) coordination to strongly bound M(2)Cl(2) units (M = Cu or Ag) where two chlorine atoms bridge the two metal atoms thus having the formal coordination number of three for copper or silver.

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PubMed2003

The molecular structure of different species of cuprous chloride from gas-phase electron diffraction and quantum chemical calculations.

The molecular geometry of gaseous cuprous chloride oligomers was determined by gas-phase electron diffraction at two different temperatures. Quantum chemical calculations were also performed for Cu(n)Cl(n) (n=1-4) molecules. A complex vapor composition was found in both experiments. Molecules of Cu(3)Cl(3) and Cu(4)Cl(4) were present at the lower temperature (689 K), while dimeric molecules (Cu(2)Cl(2)) were found in addition to the trimers and tetramers at the higher temperature (1333 K). All Cu(n)Cl(n) species were found to have planar rings by both experiment and computation. The bond lengths from electron diffraction (r(g)) at 689 K are 2.166+/-0.008 A and 2.141+/-0.008 A and the Cu-Cl-Cu bond angles are 73.9+/-0.6 degrees and 88.0+/-0.6 degrees for the trimer and the tetramer, respectively. At 1333 K the bond lengths are 2.254+/-0.011 A, 2.180+/-0.011 A, and 2.155+/-0.011 A, and the Cu-Cl-Cu bond angles 67.3+/-1.1 degrees, 74.4+/-1.1 degrees, and 83.6+/-1.1 degrees for the dimer, trimer, and tetramer, respectively.

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PubMed2002

Properties of small- to medium-sized mercury clusters from a combined ab initio, density-functional, and simulated-annealing study.

Relativistic coupled-cluster and second-order many-body perturbation theories were used to construct two- and three-body potentials for the interaction between mercury atoms. A subsequent combined simulated-annealing downhill simplex and conjugate gradient-optimization procedure gave global minima for mercury clusters with up to 30 atoms. The calculations reveal magic cluster numbers of 6, 13, 19, 23, 26, and 29 atoms. At these cluster sizes, the static dipole polarizability obtained from density-functional theory has a minimum. The calculations also reveal a fast convergence of the polarizability towards the bulk limit in contrast to the singlet-triplet gap or the ionization potential.

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PubMed2002

Experimental and theoretical studies of diatomic gold halides.

The diatomic gold halides AuX are studied by means of Fourier-transform ion cyclotron resonance mass spectroscopy and ab initio theory at a quasi-relativistic CCSD(T) level of theory. A thermokinetic approach is used to determine the bond-dissociation energies of neutral AuCl, AuBr, and AuI as well as cationic AuI+, i.e., D(0)(Au-Cl) = 66 +/- 3 kcal/mol, D(0)(Au-Br) = 50 +/- 5 kcal/mol, as well as the brackets 52 kcal/mol < D(0)(Au-I) < 64 kcal/mol and 54 kcal/mol < D(0)(Au+-I) < 66 kcal/mol at 0 K. These values allow an evaluation of previous experimental and theoretical data concerning diatomic gold halides.

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PubMed1997

Trends in Inversion Barriers of Group 15 Compounds. 3. Are Fluorinated Pyridone Derivatives Planar or Nonplanar?

Fluorinated compounds of 4-pyridone are studied using the semiempirical PM3 method, and the ab initio HF and MP2 methods. The perfluorinated derivative of 4-pyridone is predicted to have a nonplanar ring structure with the fluorine ligand at the nitrogen atom lying above the pyridine ring. The inversion barrier for the pentafluoro-4-pyridone is predicted to be 26 kJ/mol similar to that found for NH(3). This distortion corresponds to a static second-order Jahn-Teller effect and is expected to be experimentally detectable at low temperatures. N-Fluoro-4-pyridone is predicted to be nonplanar and has a small inversion barrier of 0.2 kJ/mol at the MP2 level. However, the maximum point of this barrier lies below the lowest zero-point out-of-plane inversion vibrational mode ((1)/(2) 84 cm(-1) identical with 0.5 kJ/mol). This corresponds to a dynamic Jahn-Teller effect and thus is experimentally difficult to verify. The MP2 calculations indicate that at least one fluorine atom is required at the ring nitrogen in order to achieve nonplanarity. Schleyer's negative-independent chemical shift method (NICS) is applied, and the results are used to discuss aromaticity in fluorinated pyridones. The NICS values show that succesive fluorination increases aromaticity. The vibrational spectra of all fluorinated pyridone derivatives are predicted. The vibrational spectrum of 4-pyridone is discussed in detail using a normal-mode analysis defined within a set of nonredundant internal coordinates.

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