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Brauman, J. I.

Publications and source records attributed to Brauman, J. I..

13 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Entropy bottlenecks in ion-molecule reactions

The significance of entropy bottlenecks in dissociation and recombination pathways in the prototype ionic system CH3 + CH3(+) has been investigated. Ion-molecule systems are shown to react through an entirely different dynamics than neutral systems, due to intrinsic differences in the shapes of the relevant potential surfaces. Consequences with regard to the interpretation of experimental rate parameters in the ion-molecule area are discussed.

Dodd, J. A.↗
NASA NTRS1972

Photodetachment of an electron from selenide ion - The electron affinity and spin-orbit coupling constant for SeH.

The relative cross section for the gas phase photodetachment of an electron from SeH(-) was determined in the wavelength region 428 to 578 nm. An ion cyclotron resonance spectrometer was used to generate, trap, and detect the negative ions, and a 1000-W xenon arc lamp with a grating monochromator was employed as the light source. The cross section exhibited two sharp thresholds, whose positions remained unchanged for the photodetachment of SeD(-). As a result of these thresholds, the electron affinity and the spin-orbit coupling constant were evaluated.

Smyth, K. C.↗
NASA NTRS1972

Photodetachment of electrons from amide and arsenide ions - The electron affinities of NH2., and AsH2.

The relative cross section for the gas-phase photodetachment of electrons has been determined for NH2(-) in the wavelength region of 1195 to 1695 nm and for AsH2(-) in the region from 620 to 1010 nm. An ion cyclotron resonance spectrometer was used to generate, trap, and detect negative ions. A 1000-W xenon arc lamp with a grating monochromator was used as the light source, except for one series of experiments in which a tunable laser was employed. Single sharp thresholds were observed in both cross sections, and the following electron affinity values were determined: 0.744 (plus or minus 0.022) eV for NH2. and 1.27 (plus or minus 0.03) eV for AsH2.

Smyth, K. C.↗
NASA NTRS1972

Photodetachment of electrons from phosphide ion - The electron affinity of PH2.

Measurement of the relative cross section for photodetachment of electrons from PH2(-) in the wavelength region 725 to 1020 nm (1.71 to 1.22 eV). An ion cyclotron resonance spectrometer was used to generate, trap, and detect the negative ions, and two light sources were employed to study photodetachment: a 1000-W xenon arc lamp with a grating monochromator and a continuously tunable laser. A single sharp threshold in the cross-section curve was observed, and a detailed analysis yielded an electron affinity value of 1.25 plus or minus 0.03 eV.

Smyth, K. C.↗
NASA NTRS1971

Gas-phase acidities of binary hydrides.

The preferred direction of proton transfer in a reaction between a hydride molecule and a hydride ion was studied in order to determine the relative acidities of some binary hydrides. Sufficient data are presented to make clear the periodic trends in acidities and the underlying trends in other fundamental thermochemical quantities which influence acidity. The bond dissociation energies and electron affinities of the hydrides considered are listed in a table.

Brauman, J. I.↗
NASA NTRS1971

Gas-phase basicities of amines.

Relative gas-phase basicities of some aliphatic amines have been determined by ion cyclotron resonance spectroscopy. It is found that increasing alkyl substitution increases basicity if similar substituents are compared, that increases in alkyl group size also increase basicity, and that increasing degree of substitution lowers the N-H bond dissociation energy in ammonium ions. Possible origins of these defects are discussed.

Brauman, J. I.↗
NASA NTRS1971

Alkyl substituent effects on gas-phase acidities - The influence of hybridization.

Exploration of the effect on acidity of alkyl groups bonded to trigonal and digonal carbon. Some results on the relative acidities of toluene and p-xylene, and acetylene and substitute acetylenes, as determined by ion cyclotron resonance (icr) spectroscopy, are described. Some limitations of the CNDO/2 calculation method are discussed.

Brauman, J. I.↗
NASA NTRS1969

Gas-phase acidities of amines.

Relative gas phase acidities of simple aliphatic amines and ammonia noting increase in large alkyl groups substitution

Blair, L. K.↗