Academic literature on the topic 'Polyatomic aromatic hydrocarbons'

Sydney Leach will be remembered as an outstanding and inspirational scientist, an irreplaceable friend to many—artists and musicians as well as academic colleagues. He encouraged and influenced numerous scientists as a mentor. After graduating from King's College London and carrying out war work at Farnborough, he spent all his scientific life based in Paris, working principally at Orsay and, in his later years, at the Observatoire de Paris–Meudon. Sydney was a major influence in establishing chemical physics in France after World War II, founding the highly influential Laboratoire de Photophysique Moléculaire (LPPM) at Orsay, where much of his pioneering work was performed. The ‘Sydney lab’ lives on in the newly created Institut des Sciences Moléculaires d'Orsay. Early experiments often took place at the synchrotron source (ACO, Super-ACO), just a few hundred yards from LPPM. He was a pioneering advocate of synchrotron radiation, and a driving force for its use in spectroscopy and photodynamics, along with free-electron lasers, supersonic jets, coincidence spectroscopy and matrix isolation—techniques that were applied and refined over decades and used to explore fundamental processes such as photoionization, vibronic coupling and radiationless transitions. Sydney's seminal studies of polyatomic molecular ions led him towards fresh horizons in planetary atmospheric and space science. His work opened new vistas in cometary spectroscopy, polycyclic aromatic hydrocarbons, fullerenes and their possible roles in the chemistry of the interstellar medium and, finally, biologically relevant species, helping to instigate the newly developing subject of astrobiology—a perfect example of his sustained prescience in the world of science.

The mechanisms for the reaction of methyl radical with ethylamine were determined by the density functional theory using the atomic structures of the reactants, transition states and products optimized at the B3LYP/6-311++G(3df,2p) level of theory. Seven transition states were identified for the production of CH3CHNH2 + CH4 (TS1), CH3CH2NH + CH4 (TS2), CH2CH2NH2 + CH4 (TS3), CH3CH2NHCH3 + H (TS4), CH3CH2 + CH3NH2 (TS5), C2H6 + CH2NH2 (TS6) and C3H8 + NH2 (TS7) with the corresponding barriers, 9.34, 9.90, 13.46, 27.70, 39.12, 45.82 and 69.34 kcal/mol. Thermodynamics analysis and potential energy surface showed that H-abstraction pathways take place easier than NH2-, CH3–abstractions, H-substitution of the NH2 group and CH3-substitution in ethylamine. The H-abstraction in methylene group of ethylamine is the most favourable on the PES of this reaction system. Keywords Methyl, Ethylamine, B3LYP, Transition states References [1] Lobo, V., et al., Free radicals, antioxidants and functional foods: Impact on human health. Pharmacognosy Reviews, 2010. 4(8): p. 118-126.[2] Phaniendra, A., D.B. Jestadi, and L. Periyasamy, Free Radicals: Properties, Sources, Targets, and Their Implication in Various Diseases. Indian Journal of Clinical Biochemistry, 2015. 30(1): p. 11-26.[3] Slagle, I.R., D. Sarzynski, and D. Gutman, Kinetics of the reaction between methyl radicals and oxygen atoms between 294 and 900 K. The Journal of Physical Chemistry, 1987. 91(16): p. 4375-4379.[4] Rutz L., B.H., Bozzelli J. W., Methyl Radical and Shift Reactions with Aliphatic and Aromatic Hydrocarbons: Thermochemical Properties, Reaction Paths and Kinetic Parameters. American Chemical Society, Division Fuel Chemistry, 2004. 49(1): p. 451-452.[5] Peukert, S.L. and J.V. Michael, High-Temperature Shock Tube and Modeling Studies on the Reactions of Methanol with D-Atoms and CH3-Radicals. The Journal of Physical Chemistry A, 2013. 117(40): p. 10186-10195.[6] Poutsma, M.L., Extension of Structure–Reactivity Correlations for the Hydrogen Abstraction Reaction to the Methyl Radical and Comparison to the Chlorine Atom, Bromine Atom, and Hydroxyl Radical. The Journal of Physical Chemistry A, 2016. 120(26): p. 4447-4454.[7] Shi, J., et al., Kinetic mechanisms of hydrogen abstraction reactions from methanol by methyl, triplet methylene and formyl radicals. Computational and Theoretical Chemistry, 2015. 1074: p. 73-82.[8] Peukert, S.L., et al., Direct Measurements of Rate Constants for the Reactions of CH3 Radicals with C2H6, C2H4, and C2H2 at High Temperatures. The Journal of Physical Chemistry A, 2013. 117(40): p. 10228-10238.[9] Sangwan, M., E.N. Chesnokov, and L.N. Krasnoperov, Reaction CH3 + OH Studied over the 294–714 K Temperature and 1–100 bar Pressure Ranges. The Journal of Physical Chemistry A, 2012. 116(34): p. 8661-8670.[10] Tho, N.H. and N.X. Sang, Theoretical study of the addition and hydrogen abstraction reactions of methyl radical with formaldehyde and hydroxymethylene. Journal of the Serbian Chemical Society, 2018. 83: p. 10.[11] Carl, S.A. and J.N. Crowley, Sequential Two (Blue) Photon Absorption by NO2 in the Presence of H2 as a Source of OH in Pulsed Photolysis Kinetic Studies: Rate Constants for Reaction of OH with CH3NH2, (CH3)2NH, (CH3)3N, and C2H5NH2 at 295 K. The Journal of Physical Chemistry A, 1998. 102(42): p. 8131-8141.[12] Gray, P. and A. Jones, Methyl radical reactions with ethylamine and deuterated ethylamines. Transactions of the Faraday Society, 1966. 62(0): p. 112-119.[13] Brinton, R.K. and D.H. Volman, Decomposition of Di‐t‐butyl Peroxide and Kinetics of the Gas Phase Reaction of t‐butoxy Radicals in the Presence of Ethylenimine. The Journal of Chemical Physics, 1952. 20(1): p. 25-28.[14] Brinton, R.K., The abstraction of hydrogen atoms from amines and related compounds. Canadian Journal of Chemistry, 1960. 38(8): p. 1339-1345.[15] M. J. Frisch, G.W.T., H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian 09, Revision C.01. Gaussian, Inc., Wallingford CT., 2010.[16] Hatipoglu, A., et al., Photo-oxidative degradation of toluene in aqueous media by hydroxyl radicals. Journal of Photochemistry and Photobiology A: Chemistry, 2010. 215(1): p. 59-68.[17] Eren, B. and Y. Yalcin Gurkan, Possible reaction pathways of the lincomycin molecule according to the DFT calculation method. 2017, 2017. 82(3): p. 11.[18] Becke, A.D., Density‐functional thermochemistry. II. The effect of the Perdew–Wang generalized‐gradient correlation correction. The Journal of Chemical Physics, 1992. 97(12): p. 9173-9177.[19] Becke, A.D., Density‐functional thermochemistry. I. The effect of the exchange‐only gradient correction. The Journal of Chemical Physics, 1992. 96(3): p. 2155-2160.[20] Becke, A.D., Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 1993. 98(7): p. 5648-5652.[21] Yang, W., R.G. Parr, and C. Lee, Various functionals for the kinetic energy density of an atom or molecule. Physical Review A, 1986. 34(6): p. 4586-4590.[22] Hehre W. , R.L., Schleyer P. V. R. , and Pople J. A., Ab Initio Molecular Orbital Theory. 1986, New York: Wiley.[23] Andersson, M.P. and P. Uvdal, New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p). The Journal of Physical Chemistry A, 2005. 109(12): p. 2937-2941.[24] Herzberg, G., Electronic spectra and electronic structure of polyatomic molecules, 1966, Van Nostrand: New York.[25] Sverdlov L.M., K.M.A., Krainov E. P., Vibrational Spectra of Polyatomic Molecules, 1974, Wiley: New York.[26] Hirota, E., Anharmonic potential function and equilibrium structure of methane. Journal of Molecular Spectroscopy, 1979. 77(2): p. 213-221.[27] Kuchitsu, K., Structure of Free Polyatomic Molecules. 1998: Springer-Verlag Berlin Heidelberg.[28] Hamada, Y., et al., Molecular structural of the gauche and trans conformers of ethylamine as studies by gas electron diffraction. Journal of Molecular Structure, 1986. 146: p. 253-262.[29] Goos, E.B., A.; Ruscic, B., Extended Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables. http://garfield.chem.elte.hu/Burcat/burcat.html, March, 2018.

The reaction paths of the reaction of methyl radical with propanol-2 (i-C3H7OH) were investigated in detail using density functional theory at B3LYP/6-311++G(3df,2p) level. There were seven reaction pathways which form seven products including CH4 + (CH3)2COH, CH4 + (CH3)2CHO, CH4 + CH3CHOHCH2, CH3OH + CH3CHCH3, C2H6 + CH3CHOH, (CH3)2CH-O-CH3 + H and (CH3)3CH + OH. The results of analysis of the reaction paths and thermokinetic parameters showed that methane could be generated from three different channels. The removed H-atom from secondary carbon atom in the propanol-2 molecule is the most favorable of this reaction system. Keywords Methyl, propanol-2, B3LYP, transition state References [1] I. R. Slagle, D. Sarzyński, and D. Gutman, “Kinetics of the reaction between methyl radicals and oxygen atoms between 294 and 900 K,” Journal of Physical Chemistry, 1987.[2] L. Rutz, H. Bockhorn, and J. W. Bozzelli, “Methyl radical and shift reactions with aliphatic and aromatic hydrocarbons: Thermochemical properties, reaction paths and kinetic parameters,” in ACS Division of Fuel Chemistry, Preprints, 2004.[3] N. H. Tho and N. X. Sang, “Theoretical study of the addition and hydrogen abstraction reactions of methyl radical with formaldehyde and hydroxymethylene,” J. Serb. Chem. Soc.; OnLine First - OLF, 2018.[4] D. Ferro-Costas et al., “The Influence of Multiple Conformations and Paths on Rate Constants and Product Branching Ratios. Thermal Decomposition of 1-Propanol Radicals,” Journal of Physical Chemistry A, p. 4790−4800, 2018.[5] M. T. Holtzapple et al., “Biomass Conversion to Mixed Alcohol Fuels Using the MixAlco Process,” Applied Biochemistry and Biotechnology, 1999.[6] C. R. Shen and J. C. Liao, “Metabolic engineering of Escherichia coli for 1-butanol and 1-propanol production via the keto-acid pathways,” Metabolic Engineering, 2008.[7] A. Frassoldati et al., “An experimental and kinetic modeling study of n-propanol and iso-propanol combustion,” Combustion and Flame, vol. 157, pp. 2–16, 2010.[8] M. Z. Jacobson, “Effects of ethanol (E85) versus gasoline vehicles on cancer and mortality in the United States,” Environmental Science and Technology, 2007.[9] P. Gray and A. A. Herod, “Methyl radical reactions with ethanol and deuterated ethanols,” Transactions of the Faraday Society, 1968.[10] Z. F. Xu, J. Park, and M. C. Lin, “Thermal decomposition of ethanol. III. A computational study of the kinetics and mechanism for the CH3+C2H5OH reaction,” Journal of Chemical Physics, 2004.[11] N. H. Tho and D. T. Quang, “Nghiên cứu lý thuyết đường phản ứng của gốc metyl với etanol,” Vietnam Journal of Chemistry, vol. 56, no. 3, pp. 373–378, Jun. 2018.[12] N. H. Tho and N. X. Sang, “Kinetics of the Reaction of Methyl Radical with Methanol,” VNU Journal of Science: Natural Sciences and Technology; Vol 34 No 1DO - 10.25073/2588-1140/vnunst.4725 , Mar. 2018.[13] T. W. Shannon and A. G. Harrison, “The reaction of methyl radicals with methyl alcohol,” Canadian Journal of Chemistry, vol. 41, pp. 2455–2461, 1963.[14] S. L. Peukert and J. V. Michael, “High-temperature shock tube and modeling studies on the reactions of methanol with d-atoms and CH3-radicals,” Journal of Physical Chemistry A, 2013.[15] P. Gray and A. A. Herod, “Methyl radical reactions with isopropanol and methanol, their ethers and their deuterated derivatives,” Transactions of the Faraday Society, 1968.[16] A. D. Becke, “Density functional thermochemistry. I. The effect of the exchange only gradient correction,” Journal of Chemical Physics, vol. 96, p. 2155, 1992.[17] A. D. Becke, “Density-functional thermochemistry. II. The effect of the Perdew-Wang generalized-gradient correlation correction,” The Journal of Chemical Physics, vol. 97, p. 9173, 1992.[18] A. D. Becke, “Density-functional thermochemistry. III. The role of exact exchange,” The Journal of Chemical Physics, vol. 98, p. 5648, 1993.[19] W. Yang, R. G. Parr, and C. Lee, “Various functionals for the kinetic energy density of an atom or molecule,” Physical Review A, vol. 34 (6), pp. 4586–4590, 1986.[20] W. J. Hehre, L. Radom, P. V. R. Schleyer, and J. A. Pople, Ab Initio Molecular Orbital Theory. 1986.[21] M. P. Andersson and P. Uvdal, “New scale factors for harmonic vibrational frequencies using the B3LYP density functional method with the triple-zeta basis set 6-311+G(d,p).,” The journal of physical chemistry. A, vol. 109, pp. 2937–2941, 2005.[22] Frisch, M. J.; Trucks, G. W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J. R., M. Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, J. L. Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, T. Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, and Y. . et al. Honda, “Gaussian 09 Revision C.01, Gaussian Inc. Wallingford CT.,” Gaussian 09 Revision C.01. 2010.[23] G. Herzberg, Electronic Spectra and Electronic Structure of Polyatomic Molecules. 1966.[24] L. M. Sverdlov, M. A. Kovner, and E. P. Krainov, Vibrational spectra of polyatomic molecules. New York; Chichester; Jerusalem; London: Wiley ; Israel Program for Scientific Translations, 1974.[25] E. Hirota, “Anharmonic potential function and equilibrium structure of methane,” Journal of Molecular Spectroscopy, vol. 77, pp. 213–221, 1979.[26] P. Venkateswarlu and W. Gordy, “Methyl alcohol. II. Molecular structure,” The Journal of Chemical Physics, 1955.[27] E. . B. Goos A.; Ruscic, B., “Extended Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables,” http://garfield.chem.elte.hu/Burcat/burcat.html August-2018.

This thesis is an effort to understand electronic structure and optical properties of low-dimensional conjugated molecules such as polyatomic aromatic hydrocarbons and nanoribbons composed of perylene monomers in addition to transport and magnetic properties of model conjugated systems such as ladders and junctions. we carry out a systematic study of the electronic states of several PAHs using the PPP model which incorporates long-range electron correlations. In all the molecules studied by us, we find that the 2A state is below the 1B state and hence none of them will be fluorescent in the gaseous phase. The singlet-triplet gap is more than one-half of the singlet-singlet gap in all cases and hence none of these PAHs can be candidates for improved solar cell efficiencies in a singlet fission. We discuss in detail the properties of the electronic states which include bond orders and spin densities (in triplets) of these systems