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  • 1
    Electronic Resource
    Electronic Resource
    Origin of the temperature-dependent product variation in carbene reaction with alcohol (1985)
    s.l. : American Chemical Society
    Journal of the American Chemical Society 107 (1985), S. 1940-1946 
    Details
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ja00293a024
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  • 2
    Electronic Resource
    Electronic Resource
    Prefulvene as a stable intermediate at the potential energy surface minimum of the benzene .dblharw. benzvalene isomerization process (1984)
    s.l. : American Chemical Society
    Journal of the American Chemical Society 106 (1984), S. 6751-6755 
    Details
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ja00334a047
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  • 3
    Electronic Resource
    Electronic Resource
    Epitaxial growth mechanism of diamond crystal in methane-hydrogen plasma (1986)
    s.l. : American Chemical Society
    Journal of the American Chemical Society 108 (1986), S. 5780-5783 
    Details
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ja00279a019
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  • 4
    Electronic Resource
    Electronic Resource
    On the primary process in the plasma-chemical and photochemical vapor deposition from silane. Mechanism of the radiative species SiH*(A 2Δ) formation (1986)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 2808-2813 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio molecular orbital–configuration-interaction (CI) calculations at full valence CI level as well as at the SDTQ-CI level on valence and Rydberg MOs were carried out on the potential energy hypersurfaces in the lower singlet states along one probable reaction path of the decomposition from SiH4 to 2SiH+2H+1H2. The result shows that there exists a one-step decomposition route which forms the radiative species SiH*(A 2Δ) from SiH4 spontaneously. The adiabatic potential energy hypersurfaces following the reaction path explain straightforwardly various observations in the plasma- and photo-CVD experiments of SiH4. The generation routes of SiH in other lower excited states were also clarified.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.451038
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  • 5
    Electronic Resource
    Electronic Resource
    On the primary process in the plasma-chemical and photochemical vapor deposition from silane. III. Mechanism of the radiative species Si*(1P 0) formation (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 6822-6829 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The mechanism of the radiative species Si*(1P0) formation from SiH4 was investigated with ab initio molecular orbital–configuration interaction calculations on two reaction routes: (a) the simplest one-step reaction mechanism SiH4→Si+2H2 and (b) the second simplest two-step reaction mechanism SiH4→SiH2+H2→Si+2H2. The conclusions obtained are as follows: (i) the one-step mechanism (a) operates effectively in the generation of the radiative species Si*(1P0), (ii) no effective path was found for the formation of Si*(1P0) in the two-step mechanism, (iii) the radiative species Si*(1P0) originates from the fifth lowest excited singlet state 11T1 of SiH4 at the Td structure in the one-step mechanism (a), whereas the nonradiative species Si(1D) is produced spontaneously from the fourth lowest excited singlet state 11E in both reaction mechanisms of (a) and (b), (iv) the nonradiative species SiH2(11B1) is spontaneously generated from the lowest excited singlet state 11T2 of SiH4, (v) the electronic state of the radiative Si*(1P0) has Rydberg character and the emission of Si*(1P0) at 288.2 nm is approximately expressed by 3p4s(1P0)→3p2(1D) where 4s is a Rydberg atomic orbital (AO). It was also concluded that the contributions of 3d AOs are important for making a description of the quantitative energy separations among the lower lying singlet states, 1D, 1S, and 1P0 of Si atoms.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.457657
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  • 6
    Electronic Resource
    Electronic Resource
    An ab initio theoretical research on perfluorochemicals as oxygen carriers (1984)
    Springer
    Theoretical chemistry accounts 64 (1984), S. 403-413 
    Details
    ISSN: 1432-2234
    Keywords: Molecular interaction ; Basis set dependence of the stabilization energy ; Basis set superposition error ; Intermolecular force
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In order to elucidate the nature of the interaction force effected in perfluorochemical artificial blood, the basis set dependence of the stabilization energy between a model perfluorochemical and oxygen was investigated in detail. The basis set superposition error was removed in each case. The interaction was estimated to arise from dispersion forces.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00548950
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  • 7
    Electronic Resource
    Electronic Resource
    Potential-energy surfaces in the lower excited states of benzene⇌Dewar-benzene isomerization process (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 18 (1980), S. 157-164 
    Details
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Adiabatic potential-energy surfaces in the lower excited states following the benzene⇌Dewar-benzene isomerization process were calculated by the INDO/S method postulating the concerted reaction mechanism which is proved to be valid in the ground state by the calculation of the intrinsic reaction coordinate. It was concluded that the benzene molecule in the 1B1u and 1E2u excited states readily isomerizes to Dewar-benzene in the condensed phase although the quantum yield may not be large. Bryce-Smith's proposal, that the isomerization to Dewar-benzene occurs only after the intersystem crossing to the 3B1u state in benzene molecule, will not be probable; for the 3B1u route is not favorable to the isomerization in comparison with these singlet routes. However, the rearomatization of Dewar-benzene in the ground state may produce the 3B1u benzene in small yield with higher yield of the ground-state benzene. The activation energy in the rearomatization is calculated to be 19.03 kcal/mol. These conclusions are consistent with the experimental facts. Molecular orbital correlations in the isomerization and the ionization potentials of Dewar-benzene were also discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/qua.560180122
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  • 8
    Electronic Resource
    Electronic Resource
    Theoretical aspects of the radiation effects of polymers (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3759-3773 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Millar-Wall-Charlesby empirical rule of radiation effects on polymers was theoretically examined. The theoretically calculated adiabatic potential curves of the main chain scission and side chain cleavage revealed that the effects of radiation on polymers are clearly interpreted as chemical reactions in the excited states; namely, that degradation occurs when little or no activation energy is required in the main chain cleavage reaction in the excited states, or, in other words, stabilization of the excited polymer molecule leads to the main chain cleavage. Crosslinking occurs when moderate or large activation energy is required in the main chain cleavage reaction in any electronic state and little or no activation energy is needed in the C—H bond cleavage reaction in the excited states. Therefore stabilization of the excited polymer molecule leads to the formation of a polymer radical that crosslinks. It was concluded that Millar-Wall-Charlesby's rule is exact only when the shape of the adiabatic potential curve in the ground state reflects those in the excited states.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170171131
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  • 9
    Electronic Resource
    Electronic Resource
    Acid-catalyzed degradation mechanism of poly(phthalaldehyde): Unzipping reaction of chemical amplification resist (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 77-89 
    Details
    ISSN: 0887-624X
    Keywords: poly(phthalaldehyde) ; degradation mechanism ; molecular orbital theory ; activation energy of degradation ; acid catalyzed degradation ; unzipping reaction ; resist ; chemical amplification ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The acid-catalyzed degradation mechanism of chemical amplification resists based on end-capped poly(phthalaldehyde) has been elucidated by semi-empirical molecular orbital calculations. It is concluded that: (i) two different starting points exist in the degradation of end-capped poly(phthalaldehyde), the central part of the polymer as well as the polymer end; (ii) in both cases, after the first protonation, cationic hydroxyl compounds generated decompose to the identical cation intermediate, which can unzip itself to phthalaldehyde monomers successively (unzipping reaction); (iii) the hemiacetal type intermediates hardly degrade to the same intermediate without acid catalyst; (iv) the overall activation energy for the degradation reaction is less than 14 kcal/mol in all the cases. Thus, the poly(phthalaldehyde) resist can easily self-develop below 100°C, as reported in the literature. © 1997 John Wiley & Sons, Inc.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Plasma developable photoresist containing electronic excitation energy quenching system (1983)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 23 (1983), S. 993-999 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A dry developable negative working resist composition comprised of poly(methyl isopropenyl ketone) (PMIPK) and 4-methyl-2,6-di(4′-azido-benzylidene) cyclohexanone-1 was examined. The main photochemical product formed in the resist pattern was found to be a secondary amine which crosslinks PMIPK. Post-annealing forms a hydrogen-bonded product which shows a powerful electronic excitation energy quenching effect. The quencher is more powerful than the aromatic compound arising from the azide by post-annealing only. The residual resist thickness of the negative pattern is about 80 percent of the initial thickness of the coating in spite of all the azide compound remaining in the resist coating. The obtained dry developed resist pattern has a high dry etch resistance. Etchings of Si and SiO2 were performed by plasma and reactive ion etching, respectively.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760231804
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