TITLE

Conformational properties, torsional potential, and vibrational force field for methacryloyl fluoride: An ab initio investigation

AUTHOR(S)
Laskowski, Bernard C.; Jaffe, R. L.; Komornicki, Andrew
PUB. DATE
June 1985
SOURCE
Journal of Chemical Physics;6/1/1985, Vol. 82 Issue 11, p5089
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
We have examined the structure, torsional potentials, vibrational spectra, and harmonic force fields for the s-cis and s-trans isomers of methacryloyl fluoride with the aim of understanding some of the conformational properties of these molecules and their relationship to macroscopic polymer properties. The calculations have been performed at the SCF level with a split valence basis set. We find the structure to be in reasonably good agreement with experiment and as expected find the structural variations between the two isomers to be slight. However, we do suggest a reexamination of the carbonyl geometry in light of our studies. Our calculations show the energy difference between the s-cis and the s-trans isomers to be less than 1 kcal/mol at both the split valence and the split valence polarized levels, favoring the s-trans form. An examination of the torsional potential reveals that a rigid rotor approximation provides an adequate description of the motion of either the methyl group, or of the COF moiety. For the methyl group we find a barrier of 1.5 kcal/mol, with the preferred conformation having the hydrogen atom eclipsed with respect to the carbon–carbon double bond. Our best calculations show that the torsional barrier to interconvert the s-trans to the s-cis form is 7.0 kcal/mol, somewhat higher than the recent experimental values of 6.5 and 5.1 kcal/mol. This study also points out the need to include the difference in zero point energies between reactants and the transition state when evaluating torsional potentials. Our calculated vibrational spectra show the similarities and differences between these two isomers, and suggest areas where the assignments should be further examined. In particular, we suggest that some of the low frequency torsional modes deserve further scrutiny. A fit of our data to a three term Fourier series shows that we are able to reproduce the experimentally derived barrier, even though a direct determination shows that...
ACCESSION #
7608393

 

Related Articles

  • NEW SOLUBLE POLYNAPHTYLIMIDES BASED ON DERIVATIVES OF CHLORAL. KUMYKOV, R. M.; BEEV, A. A.; MIKITAEV, A. K.; RUSANOV, A. L. // Izvestiya Vysshikh Uchebnykh Zavedenii. Seriya Khimiya i Khimich;2012, Vol. 55 Issue 7, p130 

    Not previously described soluble polynaphtylimides was obtained by the reaction of 3,3'-diamino-4,4'-dihlorarilenes with aroylen bis (naphthalic anhydrides) containing dichlorethylene, simple ether and carbonyl groups. The effect of the introduction of chlorine atoms in aromatic rings,...

  • Elastic properties of degraded polypropylene. Navarro, R. F.; d'Almeida, J. R. M.; Rabello, M. S. // Journal of Materials Science;Mar2007, Vol. 42 Issue 6, p2167 

    Even though the ultimate mechanical properties of degraded polymers are widely reported in the literature, few papers dealt with the elastic properties of polymers after submitted to a degradation source. This topic is important to the understanding of the effects of degradation in polymer...

  • Radiation-modified polytetrafluoroethylene: Structure and properties. Khatipov, S. A.; Konova, E. M.; Artamonov, N. A. // Russian Journal of General Chemistry;Sep2009, Vol. 79 Issue 9, p2006 

    The scope offered by radiation technology for polytetrafluoroethylene modification was discussed. New modified materials possess enhanced antifriction and compressive parameters and are suitable for different commercial applications.

  • Selectivity enhancement for the separation of tocopherols and steroids by integration of highly ordered weak interaction sites along the polymer main chain. Mallik, Abul; Qiu, Hongdeng; Takafuji, Makoto; Ihara, Hirotaka // Analytical & Bioanalytical Chemistry;Nov2012, Vol. 404 Issue 1, p229 

    A novel alternating copolymer-based organic phase was synthesized using a new N-substituted maleimide monomer for the development of alternating copolymer-grafted silica for high-performance liquid chromatographic applications. This new monomer (DGMI) was copolymerized with octadecyl acrylate...

  • Quantum Chemical Calculations on the Interaction between Flavonol and Functional Monomers (Methacrylic Acid and 4-Vinylpyridine) in Molecularly Imprinted Polymers. Gómez-Pineda, Luis Enrique; Pina-Luis, Georgina Esther; Cortés-Romero, Carlos Martín; Palomar-Pardavé, Manuel Eduardo; Rosquete-Pina, Giselle Alicia; Díaz-García, Marta Elena; Cuán Hernández, María de los Angeles // Molecules;Jun2010, Vol. 15 Issue 6, p4017 

    Quantum chemical calculations were performed to characterize the interaction of the flavonol molecule (FL) with methacrylic acid (MAA) and 4-vinylpyridine (4VPy) in the formation of imprinted polymers. The polarizable continuum model (PCM) was used to gain insight on the type of interaction...

  • Preparation and properties of self-crosslinkable polyurethane/silane hybrid emulsion. Lai, Xiaojuan; Shen, Yiding; Wang, Lei // Journal of Polymer Research;Nov2011, Vol. 18 Issue 6, p2425 

    Self-crosslinkable polyurethane emulsion containing active carbonyl group was obtained using dihydroxyketon N-[(1,1-dimethyl-2-acetyl)ethyl]-β-dihydroxyethylamino propanamide(DDP) and 1,4-butanediol as chain extenders, isophorone diisocyanate (IPDI), polyether polyol (PTMG1000), dimethylol...

  • New monomers with trifluoromethyl and phenylphosphine oxide substituents for polynaphthylimides and polyperyleneimides. Belomoina, N.; Bulycheva, E.; Rusanov, A.; Liu, Jin-gang; Yang, Shi-yong // Doklady Chemistry;Sep2011, Vol. 440 Issue 1, p248 

    The article describes the synthesis of monomers with soluble polynaphthylimides (PNIs) and polyperyleneimides which contains phenylphosphine oxide and trifluoromethyl substituents. It states that synthesis are prepared by superelectrophilic activation of carbonyl compounds and...

  • Use of fluorescent probes to determine catalytic chain length in chemically amplified resists. Frenette, Mathieu; Ivan, Marius Gabriel; Scaiano, J. C. // Canadian Journal of Chemistry;Jun/Jul2005, Vol. 83 Issue 6/7, p869 

    Acid-catalyzed deprotection of tert-butoxycarbonyl (t-Boc) pendant groups present in a polymer film is one of the most common chemical reactions in photolithography. We present here a novel method to determine the catalytic chain length of this reaction under different development conditions. We...

  • Photodegradation of polymers, relevance for a coating chemist -- Part II. Singh, Gurpreet Onkar; Malshe, V. C. // Paintindia;May2010, Vol. 60 Issue 5, p81 

    The article discusses polymer photodegradation. The effect of morphology on photodegradation of polyethylenes is tackled. It details the photodegradation process in various polymers including poly(N-vinylcarbazole) (PVCa), polystyrene nanocomposite film and polystyrene containing carbonyl...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics