Abstract
The asymptotic interactions at large intermolecular distances are determined for two open-shell systems, H(X2S1/2) + O2 (X3∑{skg/−}) and \( O({}^3P_{j_O } ) + OH(X^2 \Pi _{\tilde \Omega } )\) for fixed values of intramolecular distances r. The electronic diabatic Hamiltonians are set up for two purposes: i) the direct diagonalization of the electronic Hamiltonian yielding two-dimensional potential energy surfaces (PES) which depend on the intermolecular distance R and the angle γ. between R and r, and ii) the incorporation of the diabatic electronic basis into the diabatic roronic basis which can be used in the construction of the roronic Hamiltonian in the total angular momentum representation. The former procedure allows one to compare the asymptotic PES with their ab initio counterparts, while the latter provides the input data for the calculation of low temperature capture rate constants within the statistical adiabatic channel model (SACM).
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Maergoiz, A.I., Nikitin E.E., Troe, J., Ushakov V.G. Classical trajectory and statistical adiabatic channel study of the dynamics of capture and unimolecular bond fission (1996) a) I. Ion-dipole capture, J. Chem. Phys. 105, 6263–6269; b) II. Ion-quadrupole capture, ibid. 6270–6276; c) III. Dipole-dipole capture, ibid. 6277–6284; (1998) d) IV. Valence interactions between atoms and linear rotors, J. Chem. Phys. 108, 5265–5280; e) V. Valence interactions between two linear rotors, ibid. 9987–9998; (2002) g) VI. Properties of transitional modes and specific rate constants k(E,J), J. Chem. Phys. 117, 4201–4213.
a) Marques, J.M.C. and Varandas, A.J.C. (2001) On the high pressure rate constants for the H/Mu+O2 addition reaction, Phys. Chem. Chem. Phys. 3, 505–507; b) Harding, L.B., Troe, J., and Ushakov, V.G. (2001) Comment, Phys. Chem. Chem. Phys. 3, 2630–2631; c) Marques, J.M.C. and Varandas, A.J.C. (2001) Reply to the comment, Phys. Chem. Chem. Phys. 3, 2632–2633.
a) Viti, S., Roueff, E., Hartquist, T.W., Pineau des Forets, G., Williams, D.A. (2001) Interstellar oxygen chemistry, Astronomy and Astrophysics, 370, 557–569; b) Koehler, S.P.K., (2002) Low-temperature reaction kinetics and dynamics of the hydroxyl radical, Diploma Thesis, Institut fuer Physikalische Chemie, Universitaet Goettingen.
Bussery, B., Umanskii, S.Ya., Aubert-Frecon, M., and Bouty, O. (1994) Exchange interaction between two O2 molecules using the asymptotic method, J. Chem. Phys. 101, 416–423.
Cade, P.E. and Wahl, A.C. (1974) Atomic Data & Nuclear Data Tables 13, 339.
Spelsberg, D., Lorenz, T., and Meyer, W. (1993) Dynamic multipole polarizabilities and long range interaction coefficients, J. Chem. Phys. 99,7845–7858.
Spelsberg, D. and Meyer, W. (1998) Ab initio dynamic dipole polarizabilities for O2, J. Chem. Phys. 109, 9802–9810.
Harding, L.B., Troe, J., and Ushakov, V.G. (2000) Classical trajectory calculations of the high pressure limiting rate constants, Phys. Chem. Chem. Phys. 2, 631–642.
Harding, L.B., private communication.
Dashevskaya, E.I., Maergoiz, A.I., Troe, J., Litvin, I., Nikitin, E.E. (2003) Low-temperature behavior of capture rate constants, J. Chem. Phys. 118, 7313–7320.
Maergoiz, A.I., Nikitin, E.E., Troe, J. (1996) Adiabatic channel study of the capture of nitrogen and oxygen molecules by an ion, Z. Phys. D36, 339–347.
Zare, R.N. (1986) Angular Momentum, Wiley, N.Y.
Varshalovich, D.A., Moskalev, A.N., and Khersonskii, V.K. (1988) Quantum Theory of Angular Momentum, World Scientific, Singapore.
Radzig, A.A. and Smirnov, B.M. (1985) Reference data on atoms, molecules and ions, Springer, Berlin.
Cade, P.E. and Huo, W.M. (1967) Electronic structure of first-row hydrides, J. Chem. Phys., 47, 614–648.
Nikitin, E.E., Ottinger, Ch., and Shalashilin, D.V. (1996) Test of the asymptotic method as applied to atom-diatom interaction potentials, Z. Phys. D36, 257–264.
Graff, M.M. and Wagner, A.F. (1990) Theoretical studies of fine-structure effects and long-range forces. J. Chem. Phys. 92, 2423–2439.
Gentry, W.R. and Giese, C.F. (1977) Long-range interactions of ions with atoms having partially filled p subshells. J. Chem. Phys. 67, 2355–2361.
Buckingham, A.D. (1967) Permanent and induced molecular moments and long-range intermolecular forces, Adv. Chem. Phys. 12,107–142.
Spelsberg, D. (1999) Dynamic multipole polarizabilities and reduced spectra for OH, J. Chem. Phys., 111, 9625–9633.
Esposti, A.D. and Werner, H.-J. (1990) OH(X2π, A2σ+)+Ar energy surfaces, J. Chem. Phys. 93, 3351–3366.
Chu, S.I., Yoshimine, M., and Liu, B. (1974) J. Chem. Phys., 61, 5389–5395.
Clary, D.C. and Werner, H.-J. (1984) Quantum calculations on the rate constant for the O+OH reaction, Chem. Phys. Letters, 112, 346–350.
Hirschfelder, J.O., Curtiss, C.F., and Bird, R.B. (1964) Molecular Theory of the Gases and Liquids, Wiley, New York.
Harding, L.B., Maergoiz, A.I., Troe, J., and Ushakov, V.G. (2000) Statistical rate theory for the HO+O↔HO2↔H+O2 reaction system, J. Chem. Phys., 113, 11019–11034.
Pastrana, M.R., Quintales, L.A.M., Brandao, J., and Varandas, A.J.C. (1990) Recalibration of a single-valued double many-body expansion potential energy surface for ground-state HO2, J. Phys. Chem. 94, 8073–8080.
Walch, S.P., Rohlfing, C.M., Melius, C.F., and Bauschlicher, Jr., C.W. (1988) Theoretical characterization of the minimum energy path for the reaction H+O2→HO2*→HO+O, J. Chem. Phys. 88, 6273–6281.
Umanskii, S.Ya. and Nikitin, E.E. (1969) Elektronenwellenfunktionen und Terme zweiatomiger Molekuele, Theoret. chim. Acta (Berl.), 13, 91–105.
Nikitin, E.E. and Umanskii, S.Ya. (1984) Theory of Slow Atomic Collisions, Springer, Berlin-Heidelberg.
Karna, S.P. (1996) Spin-unrestricted time-dependent Hartree-Fock theory, J. Chem. Phys., 104, 6590–6605.
Landau, L.D. and Lifshitz, E.M. (1977) Quantum Mechanics, Pergamon, Oxford.
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Maergoiz, A.I., Nikitin, E.E., Troe, J., Ushakov, V.G. (2004). Asymptotic Interactions Between Open Shell Partners in Low Temperature Complex Formation: The H(X2S1/2) + O2 (X3∑ − g ) and \( O({}^3P_{j_O } ) + OH(X^2 \Pi _{\tilde \Omega } )\) Systems. In: Lagana, A., Lendvay, G. (eds) Theory of Chemical Reaction Dynamics. NATO Science Series II: Mathematics, Physics and Chemistry, vol 145. Springer, Dordrecht. https://doi.org/10.1007/1-4020-2165-8_1
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DOI: https://doi.org/10.1007/1-4020-2165-8_1
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