| Chemical Laser Studies of Chemical Reaction Dynamics. |
JUL 1977 |
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| Authors:
Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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 | Chemical laser techniques have been used to analyze energy partitioning and chemical reaction dynamics in elementary bimolecular, unimolecular, and photochemical reaction systems. Several new chemical laser systems (e.g., cyanide radical molecular electronic lasers, a hydrogen cyanide polyatomic chemical laser, and a 'hot-atom' initiated bimolecular reaction laser) were discovered. A general method for the quantitative determination of product vibrational state distributions was developed and applied to many chemical laser systems. Important ... |
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| Molecular Electronic Photodissociation Laser Studies. |
JUL 1977 |
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| Authors:
Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Chemical laser experimental techniques were used to analyze features of energy partitioning and electronic branching in photochemical and bimolecular chemical reactions. Accurate population inversions were determined for two classes of reactions: (1) photodissociation (e.g., photodissociative excitation of cyanide radical by photolysis of CH3NC) and (2) bimolecular exchange (e.g., F + HI yields HF(v)+I). New lasing transitions of the cyanide radical molecular electronic laser were obtained. In addition, energy redistribution processes ... |
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| A New Empirical Potential Hypersurface for Bimolecular Reaction Systems. |
1977 |
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| Authors:
Oded Kafri; Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| A fully empirical procedure for generating chemically accurate potential hypersurfaces for triatomic bimolecular reaction systems is described and applied to the H3 system. (Author) |
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| Ionization Processes Relevant to the Formation of New Materials. |
31 AUG 1975 |
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| Authors:
Harlan L. Goering; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| This research program involved investigation of the structure and chemistry of intermediates in ionic reactions (viz. carbonium ion reactions). The approach has been to determine symmetry properties of product forming intermediates and from these deduce structural details of these intermediates. Kinetic, isotope tracer and stereochemical methods were used. In connection with the latter a new technique was developed which involves the use of optically active nmr shift reagents for the ... |
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| Chemical Laser Studies of Energy Partitioning in Photochemical and Unimolecular Reactions. |
APR 1975 |
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| Authors:
Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Chemical laser techniques have been used to analyze energy partitioning and reaction dynamics in photochemical and unimolecular reactions which yield vibrationally excited hydrogen halide products. Six new unimolecular reaction chemical lasers and fifteen new photochemical lasers have been discovered. A general method for the quantitative determination of product vibrational state distributions has been developed and applied to many of the new lasers in addition to well-known chemical laser systems. Patterns ... |
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| Chemical Laser Studies of Energy Partitioning into Chemical Reaction Products. |
OCT 1974 |
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| Authors:
Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Chemical laser techniques for the determination of energy partitioning into individual degrees-of-freedom of chemical reaction products are reviewed. Selected studies are described and, in addition, all energy partitioning results derived from chemical laser investigations of bimolecular, unimolecular, and photochemical reactions (complete through December, 1973) are tabulated. |
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| Chemical Laser Studies of Unimolecular Reaction Dynamics. |
05 JUN 1974 |
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| Authors:
Eric R. Sirkin; Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Measurements of hydrogen fluoride vibrational state populations in several unimolecular elimination laser systems indicate that 10-15% of the reaction exoergicity is channeled into HF vibration. The mode of reactant formation influences energy partitioning in CH3CH2F(+) decomposition. (Author) |
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| The Chloroethylene Photochemical Lasers: Vibrational Energy Content of the HCl Molecular Elimination Products. |
JUN 1974 |
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| Authors:
Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Chemical laser techniques have been used to determine relative photochemical product yields and HCl (v' < or = 4) photoelimination product vibronic state distributions resulting from chloroethylene (CH2 = CHCl, CH2 = CDCl, CH2 = CCl2, cis-and trans-CHCl = CHCl, and CHCl = CCl2) photolyses. The observed highly non-statistical product vibronic state distributions are successfully matched by a bootstrap reaction dynamics model which considers sudden structural distortion and intramolecular relaxation ... |
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| Organosilicon Chemistry Related to Novel Materials. |
1974 |
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| Authors:
Robert West; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Highlights of four years of research are described in four main areas which were investigated. These areas are (1) permethylpolysilanes, (2) polylithium compounds and their polysilicon derivatives, (3) organosilyl radicals, and (4) anionic rearrangements. (Author) |
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| New Metalloboranes. (Mn(CO)3(B9H13))- and Mn(CO)3(B9H12(OC4H8)). |
MAR 1973 |
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| Authors:
John W. Lott; Donald F. Gaines; H. Shenhav; R. Schaeffer; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Two examples of a new class of air-stable metalloboranes are reported. An X-ray study of Mn(CO)3(B9H12(OC4H8)) verifies a decaborane-like structure in which the Mn(CO)3 moiety occupies a boron position. (Author) |
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| The Synthesis and Molecular Structure of a Metalloborane 'Zwitterion' Mn(CO)3(B9H12(O(CH2)4N(C2H5)3)). |
MAR 1973 |
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| Authors:
Donald F. Gaines; John W. Lott; Joseph C. Calabrese; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Reaction of Mn(CO)3(B9H12(THF)) with triethylamine produces the zwitterion Mn(CO)3(B9H12(O(CH2)4N(C2H5)3)), the structure of which has been determined by X-ray crystallography. (Author) |
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| The Formyl Fluoride Photochemical Laser: Photochemistry and Energy Content of the HF Photoelimination Product. |
MAR 1973 |
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| Authors:
Daniel E. Klimek; Michael J. Berry; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Photolysis lamda > 1650A) of formyl fluoride (HFCO) leads to HF infrared laser emission. The energy content of the HF photoelimination primary product is only a small fraction (about 7%) of the available excess energy. Fluorine atoms may also be produced as primary photochemical products. (Author) |
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| Ion Fragmentation of Organic Materials by Photoionization and Electron Impact. |
JAN 1973 |
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| Authors:
James W. Taylor; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| The work accomplished during the grant period from January, 1969 through December, 1972, is described by publication titles and titles of talks. Continuing work is described in brief form along with a list of theses and dessertations started during the grant period. (Author) |
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| Trimethylgallium. |
DEC 1971 |
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| Authors:
Donald F. Gaines; JorJan Borlin; E. P. Fody; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| The synthesis of (CH3)3Ga in good yield was conveniently effected by slowly adding an excess of (CH3)3Al to GaCl3. The (CH3)3Ga was then purified by fractional distillation. (Author) |
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| Internal Exchange in New Group III Metalloborane Derivatives. (CH3)2ALB3H8 and (CH3)2GaB3H8. |
DEC 1971 |
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| Authors:
Donald F. Gaines; JorJan Borlin; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Reaction of (CH3)2AlCl and (CH3)2GaCl with salts of the B3H8(-) anion produces (CH3)2AlB3H8 and (CH3)2GaB3H8, respectively, in good yields. The nmr spectral characteristics are unusual and suggest several internal exchange processes. (Author) |
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| Stereochemical Aspects of Ionization Processes. |
NOV 1970 |
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| Authors:
Harlan L. Goering; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| The research involved investigations of the amount and stereochemistry of ion-pair return associated with solvolytic reactions of alkyl p-nitrobenzoates and p-toluenesulfonates. One group of experiments involved determining the amount of carboxyl and sulfonate oxygen scrambling associated with ion-pair return. In these studies amounts of oxygen equilibration were compared with the amounts of total return. The objective of these experiments was to determine if oxygen equilibration is a reliable criterion for ... |
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| ISOLATION AND CHARACTERIZATION OF TWO NEW ISOMERS OF (B5H8)2. |
01 SEP 1970 |
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| Authors:
Donald F. Gaines; Terry V. Iorns; Elna M. Clevenger; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| A Description of the isolation and characterization of 2-(2'-pentaboran(9)yl)pentaborane(9), 2,2'-(B5H82, and 1-(2'-pentaboran(9)yl)pentaborane(9), 1,2'(B5H8)2, from the low volatility residues found in pentaborane(9). (Author) |
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| 1-SILYL DERIVATIVES OF PENTABORANE (9). |
JUN 1970 |
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| Authors:
Donald F. Gaines; Terry V. Iorns; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| It was found that gas phase thermolysis of mu-(CH3)3SiB5H8 at about 80C results in irreversible formation of 2-(CH3)3SiB5H8 at a reasonable rate. At higher temperatures further isomerization occurs to produce 1-(CH3)3SiB5H8. This isomerization, however, is reversible and 1-(CH3)3SiB5H8 predominates by a factor of about 3.3 at 120C. Gas phase thermolysis of 2-H3SiB5H8 at 150C results in a similar conversion to 1-H3SiB5H8. This isomerization also appears to be reversible. (Author) |
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| NOVEL ORGANOMETALLIC COMPOUNDS. |
FEB 1970 |
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| Authors:
Robert West; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| The compound C5Li4 was synthesized from methyldiacetylene and n-butyllithium. Reaction of C5Li4 with trimethylchlorosilane yielded tetrakis(trimethylsilyl)pentadieneyne, a possible monomer for heat-stable polymers. The first cage polysilane permethyloctasilabicyclo-2,2,2-octane, was prepared. Acetonitrile was lithiated to Li2CHCN, which reacts with chlorosilanes to give novel trisilylynamines. A new anionic rearrangement reaction of alkoxysilanes to silylcarbinol anions was discovered. (Author) |
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| THERMOLYSIS STUDIES OF GROUP IV DERIVATIVES OF PENTABORANE (9). |
02 OCT 1969 |
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| Authors:
Donald F. Gaines; Terry V. Iorns; Jeffrey Ullman; Elna Clevenger; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| The report concerns the thermolysis products obtained from Group IV derivatives of pentaborane of the general type R3M(IV)B5H8 (where R = H or CH3, and M(IV) = Si or Ge). Significant yields of CB5H9 are isolated from thermolysis of (CH3)3GeB5H8. Direct gas phase reaction of GeH4 with B5H9 produces 2-H3GeB5H8. (Author) |
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| CHEMISTRY OF STRAINED OLEFINS. |
01 JUN 1969 |
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| Authors:
Jerome A. Berson; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Final report on studies concerned with the experimental tests of theory in bond breaking reactions of strained ring compounds. The first test of orbital symmetry control of a thermal 1,3-sigmatropic rearrangement was established. Preliminary work was carried out on the construction of a test in the 1,5-sigmatropic case. New synthetic approaches have been developed to the optically active cycloheptatrienes needed for stereochemical experiments. (Author) |
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| STRUCTURAL CHEMISTRY AND BONDING IN INORGANIC COMPOUNDS. |
DEC 1968 |
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| Authors:
Lawrence F. Dahl; WISCONSIN UNIV MADISON DEPT OF CHEMISTRY
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| Systematic structural investigations not only have led to the characterization of new general types of organometallic complexes but also have provided new structural and bonding principles. These investigations have included studies on a wide variety of unusual organo (transition metal sulfur complexes). It has been shown that a sulfur atom can function as a doubly-bridging two-electron donating group, a triply-bridging four-electron donating group, a quadruply bridging four-electron donating group, and ... |
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Reports by Corporate Author
