@article {538,
title = {Microwave spectra, geometries, and hyperfine constants of OCAgX (X = F, Cl, Br)},
journal = {Inorganic Chemistry},
volume = {41},
number = {5},
year = {2002},
note = {ISI Document Delivery No.: 528TMTimes Cited: 17Cited Reference Count: 49},
month = {Mar},
pages = {1236-1244},
type = {Article},
abstract = {A pulsed jet cavity Fourier transform microwave spectrometer has been used to measure the rotational spectra of OCAgX (X = F, Cl, Br) in the frequency range 5-22 GHz, Metal atoms were generated via laser ablation and were allowed to react with CO and a halide precursor, prior to stabilization of the products within a supersonic jet of argon. These are the first experimental observations of OCAgF and OCAgBr, and the first high resolution spectroscopic study of OCAgCl. All three molecules are linear, Accurately determined rotational constants have been used to evaluate the various internuclear distances, which are found to be consistent with trends established for OCAuX and OCCuX species. The C-O distances are short, and the M-C distances are significantly longer than those in other molecules containing a metal-carbonyl bond, Precise values of centrifugal distortion constants and halogen nuclear quadrupole coupling constants have also been determined. The coupling constants are compared with the results of previous studies of OCCuX and OCAuX and are used to infer trends in the electron distributions of the molecules. Ab initio calculations have been performed and employed to predict the geometries, vibrational frequencies, and Mulliken valence orbital populations of the various species.},
keywords = {2ND, ATOMS, COMPLEXES, CORRELATED MOLECULAR CALCULATIONS, CU(CO)CL, GAUSSIAN-BASIS SETS, LASER-ABLATION},
isbn = {0020-1669},
url = {://000174259300031},
author = {Walker, N. R. and Gerry, M. C. L.}
}
@article {540,
title = {The microwave spectrum and structure of KrAgF},
journal = {Journal of Molecular Structure},
volume = {612},
number = {2-3},
year = {2002},
note = {ISI Document Delivery No.: 573UATimes Cited: 22Cited Reference Count: 27Sp. Iss. SI},
month = {Jul},
pages = {109-116},
type = {Article},
abstract = {The microwave spectrum of KrAgF has been assigned between 8-18 GHz, using a cavity pulsed-jet Fourier transform microwave spectrometer. The structure of the molecule has been calculated from the measured rotational constants of four isotopomers. Values for the Kr-Ag and Ag-F bond lengths of similar to2.594 and similar to1.957 Angstrom respectively have been determined. A small centrifugal distortion constant (similar to0.3 kHz) indicates that the molecule is comparatively rigid. The stretching frequency and dissociation energy of the Kr-Ag bond have been subjected to ab initio calculation at the MP2 level, yieling results of similar to113 cm(-1) and similar to32 kJ mol(-1) respectively. A Mulliken orbital population analysis suggests that the Kr-Ag bond is weakly covalent in nature. All parameters are found to be consistent with trends established for ArMX and KrMX species. (C) 2002 Elsevier Science B.V. All rights reserved.},
keywords = {ab initio calculation, CL, CONSTANTS, CORRELATED MOLECULAR CALCULATIONS, GAUSSIAN-BASIS SETS, HYPERFINE, KR, microwave spectrum, STABILITY, structure of KrAgF},
isbn = {0022-2860},
url = {://000176848500006},
author = {Walker, N. R. and Reynard, L. M. and Gerry, M. C. L.}
}
@article {5216,
title = {Fourier transform microwave spectroscopy of cyanides and isocyanides of Al, Ga, and In},
journal = {Journal of Molecular Spectroscopy},
volume = {209},
number = {2},
year = {2001},
note = {ISI Document Delivery No.: 490JPTimes Cited: 22Cited Reference Count: 44},
month = {Oct},
pages = {178-191},
type = {Article},
abstract = {Microwave spectra of the three Group 13 metal cyanide pairs AlNC/AlCN, GaNC/GaCN, and InNC/InCN have been measured in the frequency range 6-25 GHz using a pulsed jet cavity Fourier transform microwave spectrometer. The molecules were prepared by ablating the metal with a pulsed Nd:YAG laser and allowing the vapor to react with cyanogen or acetonitrile contained in the Ar backing gas of the jet. The spectra are those of linear molecules. Rotational constants. centrifugal distortion constants. and nuclear quadrupole coupling constants have been precisely evaluated. Molecular geometries determined from the rotational constants using a linear model have revealed unexpectedly short NC bond lengths for the isocyanides, MNC, and are interpreted in terms of a broadened potential well for the bending mode of these molecules. This interpretation is confirmed with ab initio calculations. The centrifugal distortion constants are consistent with this picture. A new formulation of the rigid bender model has produced plausible values for bond lengths and bending amplitudes for the isocyanides. The N-14 quadrupole coupling constants are discussed in terms of the approximate bending amplitudes. A description of the bonding in the molecules has been obtained using Townes-Dailey theory. (C) 2001 Academic Press.},
keywords = {aluminum, ATOMS, CORRELATED MOLECULAR CALCULATIONS, EQUILIBRIUM, GAUSSIAN-BASIS SETS, IRC+10216, MONOCYANIDES, PARAMETERS, SPECTRUM, STRUCTURE, TRENDS},
isbn = {0022-2852},
url = {://000172049000004},
author = {Walker, K. A. and Evans, C. J. and Suh, S. H. K. and Gerry, M. C. L. and Watson, J. K. G.}
}
@article {5217,
title = {Microwave spectra, geometries, and hyperfine constants of OCCuX (X = F, Cl, Br)},
journal = {Inorganic Chemistry},
volume = {40},
number = {24},
year = {2001},
note = {ISI Document Delivery No.: 492RMTimes Cited: 14Cited Reference Count: 45},
month = {Nov},
pages = {6158-6166},
type = {Article},
abstract = {A pulsed jet cavity Fourier transform microwave spectrometer has been used to measure the rotational spectra of OCCuX (X = F, Cl, Br) in the frequency range 5-21 GHz. Metal atoms were generated via laser ablation and were allowed to react with CO and a halide precursor, prior to stabilization of the products within a supersonic jet. These are the first experimental observations of OCCuF and OCCuBr and the first high-resolution spectroscopic study of gas-phase OCCuCl. All three molecules were found to be linear. Rotational constants, centrifugal distortion constants, nuclear quadrupole coupling constants, and nuclear spin-rotation coupling constants have been precisely determined. The rotational constants have been used to evaluate the various bond lengths, and the results are in good agreement with the trend established for OCAuX species. The C-O distance is found to be comparatively short and close to that of free CO. The M-C distance is longer than that predicted by ab initio calculations, and the Cu-X distances are very similar to those observed in the corresponding metal halides. Vibrational wavenumbers have been estimated from the distortion constants and are compared with the results of various ab initio studies. Changes in the Cu, Cl, and Br nuclear quadrupole coupling constants indicate that substantial charge rearrangement takes place on coordination with CO, consistent with the formation of strong Cu-C bonds. Mulliken orbital population analyses have been performed and provide evidence of pi -back-donation from Cu in all of the species studied. The evaluated nuclear spin-rotation coupling constants have been used to estimate the Cu-63 nuclear shielding constants, sigma, and their spans (Omega) in (OCCuF)-Cu-63, (OCCuCl)-Cu-63-Cl-35, and (OCCuBr)-Cu-63-Br-79.},
keywords = {2ND, ATOMS, COMPLEXES, CORRELATED MOLECULAR CALCULATIONS, CU(CO)CL, GAUSSIAN-BASIS SETS, ROTATIONAL, SPECTRUM},
isbn = {0020-1669},
url = {://000172181400012},
author = {Walker, N. R. and Gerry, M. C. L.}
}
@article {5173,
title = {Microwave spectrum, structure, and hyperfine constants of Kr-AgCl: Formation of a weak Kr-Ag covalent bond},
journal = {Journal of Molecular Spectroscopy},
volume = {206},
number = {1},
year = {2001},
note = {ISI Document Delivery No.: 428BNTimes Cited: 29Cited Reference Count: 38},
month = {Mar},
pages = {33-40},
type = {Article},
abstract = {The pure rotational spectrum of the complex Kr-AgCl has been measured between 8-15 GHz using a cavity pulsed-jet Fourier transform microwave spectrometer. The complex was found to be linear and relatively rigid, with a Kr-Ag bond length of similar to2.641 Angstrom. The Kr-Ag stretching frequency was estimated to be 117 cm(-1). Ab initio calculations performed at the MP2 level of theory gave the geometry, vibration frequencies, Kr-Ag bond dissociation energy, and orbital populations. The Kr-Ag bond dissociation energy was estimated to be -28 kJ mol(-1). The Kr-Ag force constant and dissociation energy are greater than those of Ar-Ag in Ar-AgCl. The chlorine nuclear quadrupole coupling constants show slight changes on complex formation. Ab initio orbital population analysis shows a small shift in sigma -electron density from Kr to Ag on complex formation. The combined experimental and ab initio results are consistent with the presence of a weak Kr-Ag covalent bond. (C) 2001 Academic Press},
keywords = {ATOMS, COMPLEXES, CORRELATED MOLECULAR CALCULATIONS, DER-WAALS, FOURIER-TRANSFORM SPECTROSCOPY, GAUSSIAN-BASIS SETS, LASER-ABLATION, RAMAN, ROTATIONAL SPECTRUM, STABILITY, TRANSITION-METAL COMPLEXES},
isbn = {0022-2852},
url = {://000168441400004},
author = {Reynard, L. M. and Evans, C. J. and Gerry, M. C. L.}
}
@article {5195,
title = {PW86-PW91 density functional calculation of vertical ionization potentials: Some implications for present-day functionals},
journal = {International Journal of Quantum Chemistry},
volume = {81},
number = {1},
year = {2001},
note = {ISI Document Delivery No.: 380EFTimes Cited: 14Cited Reference Count: 50},
month = {Jan},
pages = {34-52},
type = {Article},
abstract = {A total of 181 vertical ionization potentials (VIPs) of 41 molecules were calculated by density functional theory (DFT) employing the Perdew-Wang 1986 (PW86) exchange and Perdew-Wang 1991 (PW91) correlation functionals and using the aug-cc-pV5Z basis and experimental ground-state geometries. The overall average absolute deviation (AAD) from experiment was found to be 0.55 eV and only 0.31 eV for linear molecules but 0.86 eV for nonplanar molecules. A number of VIPs were in error by over 2 eV. In particular, DFT performed most poorly when ionization was from an orbital with highly varying density gradients (which arise from the orbital{\textquoteright}s shape or compactness or through its density being distributed over a number of atoms). Indications are that many or all present-day functionals suffer from the same failings. (C) 2001 John Wiley \& Sons, Inc.},
keywords = {ACCURATE, AROMATIC MOLECULES, CORRELATED MOLECULAR CALCULATIONS, DFT, EXCHANGE-ENERGY, functionals, GAUSSIAN-BASIS SETS, HE(II) PHOTOELECTRON-SPECTRA, ionization potential, ORGANIC-MOLECULES, PHOTO-ELECTRON SPECTRA, PW86, PW91, SPECTROSCOPY, WAVE-FUNCTIONS},
isbn = {0020-7608},
url = {://000165685400007},
author = {Shapley, W. A. and Chong, D. P.}
}
@article {4796,
title = {Noble gas-metal chemical bonding: the microwave spectra, structures and hyperfine constants of Ar-AuF and Ar-AuBr},
journal = {Physical Chemistry Chemical Physics},
volume = {2},
number = {18},
year = {2000},
note = {ISI Document Delivery No.: 353RKTimes Cited: 47Cited Reference Count: 33},
pages = {3943-3948},
type = {Article},
abstract = {The rotational spectra of the complexes Ar-AuF and Ar-AuBr have been observed in the frequency range 7-22 GHz using a pulsed-jet cavity Fourier transform microwave spectrometer. Both complexes are linear and rather rigid in the ground vibrational state, with the Ar-Au stretching frequency estimated as similar to 200 cm(-1). Isotopic data have been used to calculate an r(0) structure for Ar-AuBr while for Ar-AuF only an estimation of the r(0) geometry could be made. Ab initio calculations at the MP2 level of theory model the geometries and stretching frequencies well and predict an Ar-Au bond energy in Ar-AuF of similar to 60 kJ mol(-1). The Au nuclear quadrupole coupling constant changes significantly on complex formation, indicating extensive charge arrangement. This in conjunction with the large dissociation energy and ab initio results show that the Ar-Au bonds in these complexes are weakly covalent in nature.},
keywords = {ARGON, COMPLEXES, CORRELATED MOLECULAR CALCULATIONS, FOURIER-TRANSFORM SPECTROSCOPY, GAUSSIAN-BASIS SETS, NQR, RAMAN, ROTATIONAL SPECTRUM, STATES},
isbn = {1463-9076},
url = {://000089289100001},
author = {Evans, C. J. and Rubinoff, D. S. and Gerry, M. C. L.}
}
@article {4792,
title = {Noble gas-metal chemical bonding? The microwave spectra, structures, and hyperfine constants of Ar-CuX (X = F, Cl, Br)},
journal = {Journal of Chemical Physics},
volume = {112},
number = {21},
year = {2000},
note = {ISI Document Delivery No.: 315YCTimes Cited: 72Cited Reference Count: 40},
month = {Jun},
pages = {9363-9374},
type = {Article},
abstract = {The rotational spectra of the complexes Ar-CuF, Ar-CuCl, and Ar-CuBr have been observed in the frequency range 5-22 GHz using a pulsed-jet cavity Fourier transform microwave spectrometer. All the complexes are linear and rather rigid in the ground vibrational state, with the Ar-Cu stretching frequency estimated as similar to 200 cm(-1). Isotopic data have been used to calculate an r(0) structure for Ar-CuF, while for Ar-CuCl and Ar-CuBr partial substitution structures have also been obtained. To reduce zero-point vibrational effects a double substitution method (r(d)) has also been employed to calculate the structures of Ar-CuCl and Ar-CuBr. The Ar-Cu distance has been found to be rather short and to range from 2.22 Angstrom in Ar-CuF to 2.30 Angstrom in Ar-CuBr. Ab initio calculations at the MP2 level of theory model the geometries and stretching frequencies well and predict an Ar-Cu bond energy in Ar-CuF of similar to 47.3 kJ mol(-1). Large changes in the Cu nuclear quadrupole coupling constant on complex formation show that extensive charge rearrangement occurs upon formation of the complexes. This, in conjunction with the sizable dissociation energy, suggests that the Ar-Cu bonds in these complexes are weakly covalent. The rotational spectrum of CuF has also been reinvestigated to improve the hyperfine constants. (C) 2000 American Institute of Physics. [S0021-9606(00)00521-3].},
keywords = {2ND, ARGON VANDERWAALS COMPLEX, ATOMS, COMPLEXES, CORRELATED MOLECULAR CALCULATIONS, DER-WAALS, FOURIER-TRANSFORM SPECTROSCOPY, GAUSSIAN-BASIS SETS, ROTATIONAL SPECTRUM, STATES},
isbn = {0021-9606},
url = {://000087139700021},
author = {Evans, C. J. and Gerry, M. C. L.}
}
@article {4795,
title = {Noble gas-metal chemical bonds. Microwave spectra, geometries, and nuclear quadrupole coupling constants of Ar-AuCl and Kr-AuCl},
journal = {Journal of the American Chemical Society},
volume = {122},
number = {25},
year = {2000},
note = {ISI Document Delivery No.: 332CBTimes Cited: 70Cited Reference Count: 41},
month = {Jun},
pages = {6100-6105},
type = {Article},
abstract = {The pure rotational spectra of Ar-AuCl and Kr-AuCl have been measured using a pulsed-jet cavity Fourier transform microwave spectrometer. Both complexes have been found to be linear and are relatively rigid in their ground vibrational states. The noble gas-gold stretching frequencies have been estimated to be 198 and 161 cm(-1) for Ar-AuCl and Kr-AuCl, respectively. From the isotopic data obtained. ro structures have been calculated for both Ar-AuCl and Kr-AuCl, while a partial substitution (r(s)) structure has been obtained for Kr-AuCl. The Ar-Au distance has been found to be 2.47 Angstrom, while the Kr-Au distance is 2.52 Angstrom. Ab initio calculations have been performed at the MP2 level of theory on both complexes to obtain geometries, vibrational frequencies, and dissociation energies. The dissociation energies for Ar-AuCl and Kr-AuCl have been estimated to be 47 and 71 kJ mol(-1), respectively. The nuclear quadrupole coupling constant of Au has been found to change significantly on complex formation (to -259.8 MHz in Ar-AuCl, and -349.9 MHz in Kr-AuCl) from its value in the monomer unit (+9.6 MHz in AuCl), which is consistent with extensive charge rearrangement on formation of the complexes. This, in conjunction with the sizable dissociation energies, indicates that the Ar-Au and Kr-Au bonds are weakly covalent.},
keywords = {ARGON, ATOMS, CORRELATED MOLECULAR CALCULATIONS, DER-WAALS COMPLEXES, FOURIER-TRANSFORM SPECTROSCOPY, GAUSSIAN-BASIS SETS, LASER-ABLATION, RAMAN, ROTATIONAL, SPECTRUM, STATES},
isbn = {0002-7863},
url = {://000088054900021},
author = {Evans, C. J. and Lesarri, A. and Gerry, M. C. L.}
}
@article {3275,
title = {COMPLETENESS PROFILES OF ONE-ELECTRON BASIS-SETS},
journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
volume = {73},
number = {1},
year = {1995},
note = {ISI Document Delivery No.: QK176Times Cited: 21Cited Reference Count: 28},
month = {Jan},
pages = {79-83},
type = {Article},
abstract = {The completeness profile is used to provide a visual assessment of the quality of one-electron basis sets. The approach is illustrated by examples of a number of basis sets for the carbon atom. New insight is gained regarding the superiority of spin density calculations using Chipman{\textquoteright}s basis sets.},
keywords = {ATOMS, CORRELATED MOLECULAR CALCULATIONS, GAUSSIAN-BASIS SETS, HYPERPOLARIZABILITIES, INFORMATION, LOCAL-DENSITY, MOMENTUM SPACE PROPERTIES, ONE-ELECTRON BASIS SETS, ORBITALS, POLARIZABILITIES, SPIN-DENSITIES, THEORETIC APPRAISAL},
isbn = {0008-4042},
url = {://A1995QK17600011},
author = {Chong, D. P.}
}
@article {3281,
title = {DENSITY-FUNCTIONAL CALCULATIONS OF FERMI CONTACT HYPERFINE COUPLING PARAMETERS},
journal = {Chemical Physics Letters},
volume = {234},
number = {4-6},
year = {1995},
note = {ISI Document Delivery No.: QK799Times Cited: 29Cited Reference Count: 31},
month = {Mar},
pages = {405-412},
type = {Article},
abstract = {Fermi contact parameters are calculated with a range of one-particle basis sets and functionals. The parameters are determined at all nuclei in the following eleven radicals: C2H3, C2H2F, CH, NH+, NH, OH+, OH, FH, FF-, CN, NO2. Results show that using Becke{\textquoteright}s new three-parameter exchange functional leads to improved agreement with experiment.},
keywords = {ACCURATE, APPROXIMATION, CORRELATED MOLECULAR CALCULATIONS, DOUBLE-RESONANCE, EXCHANGE-ENERGY, GAUSSIAN-BASIS SETS, MAGNETIC-RESONANCE SPECTRUM, optical, SPECTROSCOPY, TRANSITION},
isbn = {0009-2614},
url = {://A1995QK79900022},
author = {Cohen, M. J. and Chong, D. P.}
}