| Автор | Aoyagi, Mutsumi |
| Автор | Shepard, Ron |
| Автор | Wagner, Albert, F. |
| Дата выпуска | 1991 |
| dc.description | Ab initio calculations of the electronic wave function and associated potential energy of CH<sub> 3</sub> at geometries appro priate for the title reaction described here allow charac terization of the reactants and the energetically most fa vorable routes that are followed during the reaction. The quantum mechanical description of the electronic mo tion at each molecular geometry involves the response of each electron to the average field of all other elec trons and the approximate correlated response of each electron to the instantaneous position of the other elec trons. The basic methodology for the computation of this wave function, using extensive orbital basis sets and large-scale configuration expansions, is described. This calculation is one of the largest ever attempted for the characterization of a polyatomic reaction path. However, the path description involves a fine balance of energy contributions that requires this level of sophistication. The calculated properties of the reactants, the interme diate CH<sub>3</sub>, and the reaction paths to form CH<sub>3</sub> are pre sented. The computed energetics compare favorably to experimental results. |
| Издатель | Sage Publications |
| Название | An Ab Initio Theoretical Study of the CH + H2 ⇉ Ch3 * ⇉ Ch2 + H Reactions |
| Тип | Journal Article |
| DOI | 10.1177/109434209100500105 |
| Print ISSN | 1094-3420 |
| Журнал | International Journal of High Performance Computing Applications |
| Том | 5 |
| Первая страница | 72 |
| Последняя страница | 89 |
| Аффилиация | Aoyagi, Mutsumi, ARGONNE NATIONAL LABORATORY ARGONNE, ILLINOIS 60439 |
| Аффилиация | Shepard, Ron, ARGONNE NATIONAL LABORATORY ARGONNE, ILLINOIS 60439 |
| Аффилиация | Wagner, Albert, F., ARGONNE NATIONAL LABORATORY ARGONNE, ILLINOIS 60439 |
| Выпуск | 1 |
| Библиографическая ссылка | Amano, T., Bernath, P.F., Yamada, C., Endo, Y., and Hirota, E.1982. Difference frequency laser spectroscopy of the v 3 band of the methyl radical. J. Chem. Phys.77:5284-5287. |
| Библиографическая ссылка | Anderson, S.M., Freedman, A., and Kolb, C.E.1987. Fast flow studies of CH radical kinetics at 290 K. J. Phys. Chem.91:6272-6277. |
| Библиографическая ссылка | Aoyagi, M., Shepard, R., Wagner, A.F., Dunning, T.H. Jr., and Brown, F.B.1990. Ab initio theoretical studies of the CH2 + H = CH3 = CH + H2 reactions. J. Phys. Chem.94:3236-3241. |
| Библиографическая ссылка | Bauschlicher, C.W. Jr., Langhoff, S.R., and Taylor, P.R.1990. Accurate quantum chemical calculations. Advances inChem. Phys.77:63-161. |
| Библиографическая ссылка | Becker, K.H., Engelhardt, B., Wiesen, P., and Bayes, K.D.1989. Rate constants for CH(x2II) reactions at low total pressures . Chem. Phys. Lett. 154:342-348. |
| Библиографическая ссылка | Begemann, M.H., Dreyfus, R.W., and Jacsinski, J.M.1989. Absolute rate constants for the reaction of SiH with hydrogen, deuterium and silane. Chem. Phys. Lett.155:351-355. |
| Библиографическая ссылка | Berman, M.R., and Lin, M.C.1984. Kinetics and mechanisms of the reactions of CH and CD with H2 and D2. J. Chem. Phys.81:5743-5752. |
| Библиографическая ссылка | Bohland, T., and Temps, F.1984. Direct determination of the rate constant for the reaction CH2 + H → CH + H2. Ber. Bunsen-ges. Phys. Chem.88:459-461. |
| Библиографическая ссылка | Bosnali, M.W., and Pemer, D.Z.1971. Studies with pulsed-radiolysis of the reaction of CH (2II) with methane and other substances. Naturforsch . 26a:1768-1769. |
| Библиографическая ссылка | Braun, W., McNesby, J.R., and Bass, A.M.1967. Flash photolysis of methane in the vacuum ultraviolet. II. Absolute rate constants for reactions of CH with methane, hydrogen and nitrogen. J. Chem. Phys.46:2071-2080. |
| Библиографическая ссылка | Brooks, B.R., and Schaefer, H.F. Iii.1977. Reactions of carbynes. Potential energy surfaces for the doublet and quartet methylidyne (CH) reactions with molecular hydrogen. J. Chem. Phys.67:5146-5151. |
| Библиографическая ссылка | Bunker, P.R., Jensen, P., Kraemer, W.P., and Beardsworth, A.1986. The potential surface of X3B1 methylene (CH 2) and the singlet-triplet splitting. J. Chem. Phys.85:3724-3731. |
| Библиографическая ссылка | Butler, J.E., Goss, L.P., Lin, M.C., and Hudgens, J.W.1979. Production, detection and reactions of the CH radical . Chem. Phys. Lett. 63:104-107. |
| Библиографическая ссылка | Caldwell, N.J., Rice, J.K., Nelson, H.H., Adams, G.F., and Page, M.1990. Theoretical and experimental investigation of the reaction B H + D2 → BHD2. J. Phys. Chem.93:479-488. |
| Библиографическая ссылка | Chase, M.W. Jr., Davies, C.A., Downey, J.R. Jr., Frurip, D.J., McDonald, R.A., and Syveruv, A.N.1985. JANAF thermochemical tables. J. Phys. Chem. Ref. Data14:I-1856. |
| Библиографическая ссылка | Cobos, C.J., and Troe, J.1985. Theory of thermal unimolecular reactions at high pressures. II. Analysis of experimental results. J. Chem. Phys.83:1010-1015. |
| Библиографическая ссылка | Dunning, T.H. Jr.1989. Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen. J. Chem. Phys.90:1007-1023. |
| Библиографическая ссылка | Dunning, T.H. Jr., Harding, L.B., Bair, R.A., Eades, R.A., and Shepard, R.L.1986. Theoretical |
| Библиографическая ссылка | studies of the energetics and mechanisms of chemical reactions: abstraction reactions. J. Phys. Chem.90:344-356. |
| Библиографическая ссылка | Frank, P., Bhaskaran, K.A., and Just, Th.1986. High temperature reactions of triplet methylene and ketene with radicals. J. Phys. Chem.90:2226-2231. |
| Библиографическая ссылка | Grebe, J., and Homann, K.H.1982. Kinetics of the species OH(A2Σ+), OH(X2II) in the system C2H2/O/H. Ber. Bunsenges. Phys. Chem.86:581-587. |
| Библиографическая ссылка | Harrison, R.J., and Zarrabian, S.1989. An efficient implementation of the full-CI method using an (n-2)-electron projection space. Chem. Phys. Lett.158:393-398. |
| Библиографическая ссылка | Hermann, H.W., and Leone, S.R.1982. Photo-fragmentation dynamics of CH3I at 248 and 266 nm: vibrational distributions in the CH3 (v 2) "umbrella" mode. J. Chem. Phys.76:4766-4774. |
| Библиографическая ссылка | Holt, P.L., McCurdy, K.E., Weisman, R.B., Adams, J.S., and Engel, P.S.1984. Transient CARS spectroscopy of the υ1 band of methyl radical. J. Chem. Phys.81:3349-3350. |
| Библиографическая ссылка | Jacox, M.E.1977. Matrix isolation study of the infrared spectrum and structure of the CH3 free radical. J. Mol. Spectrosc.66:272-287. |
| Библиографическая ссылка | Jasien, P.G., and Shepard, R.1988. A general polyatomic potential energy surface fitting method. Int. J. Quantum Chem.S22:183-198. |
| Библиографическая ссылка | Liu, K., and Macdonald, R.G.1988. State-to-state reaction dynamics: a crossed molecular beam study of the reaction CH(2II1/2; N = 1) + D2 → CD(2II1/2,3/2; N') + HD. J. Chem. Phys.89:4443-4444. |
| Библиографическая ссылка | Lohr, R., and Roth, P.1981. Shock tube measurements of the reaction behaviour of acetylene with O-atoms. Ber. Bunsenges. Phys. Chem.85:153-158. |
| Библиографическая ссылка | Macdonald, R.G., and Liu, K.1990a. A crossed-beam study of the state-resolved dynamics of collisions between CH(2II) + D2. I. The inelastic scattering channel . J. Chem. Phys. 93:2431-2442. |
| Библиографическая ссылка | Macdonald, R.G., and Liu, K.1990b. A crossed-beam study of the state-resolved dynamics of collisions between CH(2II) + D2. II. The isotope exchange channel . J. Chem. Phys. 93:2443-2459. |
| Библиографическая ссылка | Merkel, A., and Zulicke, L.1987. Nonempirical parameter estimate for the statistical adiabatic theory of unimolecular fragmentation: carbon-hydrogen bond breaking in methyl . Molecular Phys. 60:1379-1393. |
| Библиографическая ссылка | Peeters, J., and Vinckier, C.1974. Production of chemi-ions and formation of CH and CH 2 radicals in methane-oxygen and ethylene-oxygen flames. Comb. (Internat.) Symp.15:969-977. |
| Библиографическая ссылка | Roth, P., Barner, U., and Lohr, R.1979. Messugen zum Hoch temperaturzerfall des Methyl-Radikals . Ber. Bunsenges. Phys. Chem. 83:929-932. |
| Библиографическая ссылка | Shavitt, I.1988. Unitary group approach to configuration interaction calculations of the electronic structure of atoms and molecules. In Mathematical frontiers in computational and chemical physics, edited by D. G. Truhlar.Berlin: Springer-Verlag, pp. 300-349. |
| Библиографическая ссылка | Shepard, R.1987. The multiconfiguration self-consistent field method . In Advances in chemical physics, ab initio methods in quantum chemistry II, edited by K. P. Lawley. New York: Wiley, pp. 63-200. |
| Библиографическая ссылка | Shepard, R., Shavitt, I., Pitzer, R.M., Comeau, D.C., Pepper, M., Lischka, H., Szalay, P.G., Ahlrichs, R., Brown, F.B., and Zhao, J.-G.1988. A progress report on the status of the COLUMBUS MRCI program system. Internat. J. Quantum Chem.S22:149-165. |
| Библиографическая ссылка | Spirko, V., and Bunker, P.R.1982. The potential function and rotational-vibrational energy levels of the methyl radical CH3. J. Mol. Spectrosc.95:381-390. |
| Библиографическая ссылка | Yamada, C., Hirota, E., and Kawaguchi, K.1981. Diode laser study of the v2 band of the methyl radical. J. Chem. Phys.75:5256-5264. |
| Библиографическая ссылка | Zabarnick, S., Fleming, J.W., and Lin, M.C.1986. Kinetic study of the reaction CH(X2II) + H 2 CH2(X3B1) + H in the temperature range 372 to 675 K . J. Chem. Phys. 85:4373-4376. |
