A search accelerated correct intensity Fourier transform microwave spectrometer with pulsed laser ablation source.

The ablation of metal surfaces in the presence of a precursor gas produces reaction products which are often difficult to predict and highly dependent on ablation conditions. This article describes the successful development and implementation of a laser ablation source-equipped Fourier transform microwave spectrometer capable of observing 4 GHz regions of spectra in a single data acquisition event. The dramatically increased speed with which regions may be searched, when compared to other high resolution microwave techniques, allows the source conditions to be the prime variable in laser ablation microwave spectroscopic studies. A second feature of the technique is that observed spectral features have correct relative intensities. This is advantageous when assigning observed spectra. The study of two metal chlorides, AgCl and AuCl, illustrate the instrument's benefits.

Modeling and measurements of solid-liquid and vapor-liquid equilibria of polyols and carbohydrates in aqueous solution.

The solubilities of five saccharides in water have been measured at various temperatures. This includes the monosaccharides xylose and galactose, and the disaccharides maltose monohydrate, cellobiose and trehalose dihydrate. A method that uses interaction energies and interaction parameters calculated with molecular mechanics methods has shown to give good predictions of the phase behavior of a variety of mixtures, including glycols and small saccharides in aqueous solution. The method is completely predictive, as the strength of the molecular interactions is determined with a theoretical method in the absence of any phase equilibrium data. For calculating solubilities, experimental values for the melting points and the heats of fusion of the compounds under study are, however, necessary. The solubilities of the five saccharides listed above, raffinose and meso-erythritol in water were calculated with this method. The calculated solubilities are in reasonably good agreement with experiment, and in the case of meso-erythritol, which is a polyalcohol (polyol), and galactose, the agreement between prediction and experiment is excellent. Also the vapor pressures of water over several polyols and saccharides in aqueous solution have been predicted with this method, giving results in excellent agreement with the experimental values.

The pure rotational spectrum of the actinide-containing compound thorium monoxide.

The J = 1-0 pure rotational transition, together with hyperfine structure where appropriate, has been recorded for all three naturally occurring isotopomers of the actinide-containing compound thorium monoxide ((232)Th(16)O, (232)Th(17)O and (232)Th(18)O).

Oxygen-17 hyperfine structures in the pure rotational spectra of SrO, SnO, BaO, HfO and ThO.

Hyperfine structures arising from the couplings of the nuclear spin angular momentum of (17)O (I = 5/2) with the end over end rotation of several metal-containing diatomic monoxides have been observed using a Fourier transform microwave spectrometer. The molecules have been produced by reacting (17)O(2) with laser ablated metal atoms. The oxygen-17 nuclear quadrupole coupling constants have been determined for the title molecules and are interpreted in terms of a simple Townes-Dailey model. Also, the oxygen-17 nuclear spin-rotation constants have been determined and used to calculate the oxygen-17 shieldings for each molecule.

The quadrupole moment of the Sb nucleus from molecular microwave data and calculated relativistic electric-field gradients.

The recently determined accurate values of the nuclear quadrupole coupling constant of the Sb nucleus in SbN, SbP, SbF, and SbCl and the calculated electric-field gradients at Sb in these molecules are used to obtain the nuclear quadrupole moment of 121Sb and 123Sb. The calculation of the electric-field gradient has been carried out by using the infinite-order two-component relativistic method in the scalar approximation. The accompanying change of picture of the electric-field gradient operator has been accounted for by employing the shifted nucleus model of nuclear quadrupoles. The electron correlation effects are calculated at the level of the coupled cluster approximation. The present calculations give the "molecular" value of the nuclear quadrupole moment of 121Sb equal to -556+/-24 mb which is considerably different from the old "recommended" value of -360+/-40 mb and also differs from the recent "solid-state" result (-669+/-15 mb). The validation of the present data is comprehensively discussed.

The influence of nuclear volume and electronic structure on the rotational energy of platinum monoxide, PtO.

The pure rotational spectra of seven isotopic species of platinum monoxide have been measured with a cavity pulsed jet Fourier-transform microwave spectrometer. The molecules were prepared by laser ablation of Pt foil in the presence of O2 and stabilized in a supersonic jet of argon. A multi-isotopomer Dunham-type analysis of the spectra produced values for Y01 and Y11, along with unusually large values for Born-Oppenheimer breakdown (BOB) parameters for both Pt and O atoms. The values of the BOB parameters have been rationalized in terms of the molecular electronic structure and finite nuclear size (field shift) effects. A large negative 195Pt effective nuclear spin-rotation constant has been rationalized in terms of the electron-nucleus dipole-dipole hyperfine constant. Precise internuclear separations have been evaluated.

Pure rotational spectra of LuF and LuCl.

The pure rotational spectra of two isotopic species of LuF and three of LuCl have been measured in the frequency range 5-17 GHz using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laser ablation of Lu metal in the presence of SF(6) or Cl(2), and stabilized in supersonic jets of Ar. Spectra of molecules in states having v= 0, 1, and 2 have been measured, to produce rotational constants and centrifugal distortion constants, along with hyperfine constants for all the nuclei. Dunham-type fits for LuCl produced a Born-Oppenheimer breakdown parameter for Cl. Although a theoretical calculation showed that Lu in LuCl should have a significant field shift effect parameter, it could not be determined from the spectrum. Equilibrium internuclear distances, r(e), and dissociation energies have been evaluated for both molecules. The nuclear quadrupole coupling constants are discussed in terms of the molecular electronic structure.

Internuclear distance and effects of Born-Oppenheimer breakdown for PtS, determined from its pure rotational spectrum.

Platinum monosulfide PtS has been prepared in its X0(+) ground electronic state by laser ablation of Pt in the presence of H(2)S. The rotational spectra of eight isotopic species have been measured with a cavity pulsed jet Fourier-transform microwave spectrometer. Spectral analysis using a multi-isotopomer Dunham-type expression produced values for Y(01), Y(02), Y(11), and Y(21), along with large values for Born-Oppenheimer breakdown (BOB) parameters for both atoms of the molecule. The BOB parameters are rationalized in terms of the molecular electronic structure and nuclear field shift effects. A large negative (195)Pt nuclear spin-rotation constant has been rationalized in terms of the electron-nucleus dipole-dipole hyperfine constant. The equilibrium bond length in the Born-Oppenheimer approximation has been evaluated.

XeAuF.

XeAuF has been detected and characterized using microwave rotational spectroscopy. It was prepared by laser ablation of Au in the presence of Xe and SF(6), and stabilized in a supersonic jet of Ar. The spectrum was measured with a cavity pulsed jet Fourier transform microwave spectrometer, in the frequency range 6-26 GHz. Rotational constants, centrifugal distortion constants, and (131)Xe and (197)Au nuclear quadrupole coupling constants have been evaluated. The molecule is linear, with a short XeAu bond (2.54 A), and is rigid. The (131)Xe nuclear quadrupole coupling constant (NQCC) is large (-135 MHz). The (197)Au NQCC differs radically from that of uncomplexed AuF. The results are supported by those of ab initio calculations which have given an XeAu dissociation energy approximately 100 kJ mol(-1), plus Mulliken and natural bond orbital populations, MOLDEN plots of valence orbitals, and an energy density distribution. All evidence is consistent with XeAu covalent bonding in XeAuF.

Rotational spectra, structures, hyperfine constants, and the nature of the bonding of KrCuF and KrCuCl.

Rotational spectra of KrCuF and KrCuCl have been measured in the frequency range 8-18 GHz, using a pulsed jet cavity Fourier transform microwave spectrometer. The molecules were prepared by ablating Cu metal with a pulsed Nd:YAG laser (1064 nm) and allowing the plasma to react with appropriate precursors (Kr plus SF(6) or Cl(2)) contained in the backing gas of the jet (Ar or Kr). Rotational constants, internuclear distances, vibration frequencies, and (83)Kr, Cu, and Cl nuclear quadrupole coupling constants have all been evaluated. The Kr-Cu bonds are short and the complexes are rigid. The (83)Kr coupling constant of KrCuF is large (128.8 MHz). The Cu nuclear quadrupole coupling constants differ radically from those of uncomplexed CuF and CuCl molecules. The results are supported by those of ab initio calculations, which have also yielded Mulliken populations, MOLDEN plots of valence molecular orbitals and Laplace concentrations, and electron localization functions. The results are consistent with those reported earlier for other noble gas-noble metal halide complexes. The results have been used to assess the nature of the bonding in the complexes and have produced good evidence for weak noble gas-noble metal chemical bonding.

Microwave spectra and structures of KrAuF, KrAgF, and KrAgBr; 83Kr nuclear quadrupole coupling and the nature of noble gas-noble metal halide bonding.

Microwave spectra of the complexes KrAuF and KrAgBr have been measured for the first time using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laser ablation of the metal from its solid and allowing the resulting plasma to react with an appropriate precursor (Kr, plus SF6 or Br2) contained in the backing gas of the jet (usually Ar). Rotational constants; geometries; centrifugal distortion constants; vibration frequencies; and 197Au, 79Br, and 81Br nuclear quadrupole coupling constants have all been evaluated. The complexes are unusually rigid and have short Kr-Au and Kr-Ag bonds. The 197Au nuclear quadrupole coupling constant differs radically from its value in an AuF monomer. In addition 83Kr hyperfine structure has been measured for KrAuF and the previously reported complex KrAgF. The geometry of the latter has been reevaluated. Large values for the 83Kr nuclear quadrupole coupling constants have been found for both complexes. Both the 197Au and 83Kr hyperfine constants indicate a large reorganization of the electron distribution on complex formation. A thorough assessment of the nature of the noble gas-noble metal bonding in these and related complexes (NgMX; Ng is a noble gas, M is a noble metal, and X is a halogen) has been carried out. The bond lengths are compared with sums of standard atomic and ionic radii. Ab initio calculations have produced dissociation energies along with Mulliken populations and other data on the electron distributions in the complexes. The origins of the rigidity, dissociation energies, and nuclear quadrupole coupling constants are considered. It is concluded that there is strong evidence for weak noble gas-noble metal chemical bonding in the complexes.