Quantum real wave-packet dynamics of the N(S4)+NO(X̃Π2)→N2(X̃Σg+1)+O(P3) reaction on the ground and first excited triplet potential energy surfaces: Rate constants, cross sections, and product distributions

The reaction N+NO→N2+O was studied by means of the time-dependent real wave-packet (WP) method and the J-shifting approximation. We consider the ground 1A″3 and first excited 1A′3 triplet states, which correlate with both reactants and products, using analytical potential energy surfaces (PESs) recently developed in our group. This work extends our previous quantum dynamics study, and probabilities, cross sections, and rate constants were calculated and interpreted on the basis of the different shapes of the PESs (barrierless 1A″3 and with barrier 1A′3 surfaces, respectively). The WP rate constant (k1) shows a weak dependence on T(200–2500K), as the dominant contribution to reactivity is provided by the barrierless ground PES. There is a good agreement of WP k1 with the measurements and variational transition state theory (VTST) data, and also between the WP and VTST k1(1A″3) results. Nevertheless, there is a large discrepancy between the WP and VTST k1(1A′3) results. Product state distributions were also...

[1]  P. Gamallo,et al.  Ab initio study of the two lowest triplet potential energy surfaces involved in the N(4S)+ NO (X 2Π) reaction , 2003 .

[2]  T. Slanger,et al.  Measurements of vibrationally excited molecules by Raman scattering. I The yield of vibrationally excited nitrogen in the reaction N+NO → N2+O , 1973 .

[3]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[4]  Stephen K. Gray,et al.  Quantum reactive scattering calculations of cross sections and rate constants for the N(2D)+O2(X 3Σg−)→O(3P)+NO(X 2Π) reaction , 2003 .

[5]  J. Fox.  Rate Coefficient for the Reaction N + NO , 1994 .

[6]  K. P. Lim,et al.  Rate constants for the N2O reaction system: Thermal decomposition of N2O; N+NO→N2+O; and implications for O+N2→NO+N , 1992 .

[7]  I. McDermid,et al.  Mass spectrometric determinations of the rates of elementary reactions of NO and of NO2 with ground state N4S atoms , 1975 .

[8]  Kenneth R. Hall,et al.  Thermodynamic Properties of Key Organic Oxygen Compounds in the Carbon Range C1 to C4. Part 1. Properties of Condensed Phases , 1985 .

[9]  R. T. Pack.  Space‐fixed vs body‐fixed axes in atom‐diatomic molecule scattering. Sudden approximations , 1974 .

[10]  D. Weisenstein,et al.  Kinetics of reactions of ground state nitrogen atoms (4S3/2) with NO and NO2 , 1994 .

[11]  S. Gray,et al.  Quantum dynamics with real wave packets, including application to three-dimensional (J=0) D + H2 → HD + H reactive scattering , 1998 .

[12]  R. Sharma,et al.  Quasiclassical trajectory study of the N(4S)+NO(X2Π)→N2(X1Σ+g)+O(3P) reaction rate coefficient , 1996 .

[13]  D. Siskind,et al.  Nitric oxide in the middle to upper thermosphere , 1992 .

[14]  Raymond W. Walker,et al.  Evaluated kinetic data for combustion modelling supplement I , 1994 .

[15]  Joel M. Bowman,et al.  Reduced dimensionality theory of quantum reactive scattering , 1991 .

[16]  P. Gamallo,et al.  Quantum wave packet dynamics of the 1 3A″ N(4S)+NO(X̃ 2Π)→N2(X̃ 1Σg+)+O(3P) reaction , 2003 .

[17]  P. Gamallo,et al.  Ab initio derived analytical fits of the two lowest triplet potential energy surfaces and theoretical rate constants for the N(4S)+NO(X 2Π) system , 2003 .

[18]  G. Schatz,et al.  Probing the effect of the H2 rotational state in O(1D)+H2→OH+H: Theoretical dynamics including nonadiabatic effects and a crossed molecular beam study , 2000 .

[19]  P. Gamallo,et al.  Product distributions, rate constants, and mechanisms of LiH+H reactions. , 2005, The Journal of chemical physics.

[20]  R. Levine,et al.  Molecular Reaction Dynamics and Chemical Reactivity , 1987 .

[21]  M. Molina,et al.  Chemical kinetics and photochemical data for use in stratospheric modeling , 1985 .

[22]  Miguel González,et al.  Quantum dynamics of the N(4S)+O2 reaction on the X 2A′ and a 4A′ surfaces: Reaction probabilities, cross sections, rate constants, and product distributions , 2002 .