Photodissociation of triatomic molecules: Rotational scattering effectsa)

An exact quantum method for calculating the state‐to‐state direct photodissociation probabilities for arbitrary (linear or bent) triatomic molecules is presented. It is shown that this method, which requires the accumulation of Franck–Condon overlap integrals between the initial state and a scattering state satisfying arbitrary scattering boundary conditions, is equivalent to the solution of the driven equations of Band, Freed, and Kouri. For both HCN and ICN the effects of variation of the final state potential on the vibrational and rotational distributions of the CN fragments are examined. Agreement of our exact calculations with the approximate calculations of Morse and Freed is very good.

[1]  M. Shapiro,et al.  Photofragmentation of triatomic molecules. Theory of angular and state distribution of product fragments , 1981 .

[2]  M. Gordon,et al.  Expansion approach to photodissociation dynamics. I. Theory , 1981 .

[3]  K. Freed,et al.  Rotational and angular distributions from photodissociations. III. Effects of dynamic axis switching in linear triatomic molecules , 1981 .

[4]  D. Kouri,et al.  Half‐collision description of final state distributions of the photodissociation of polyatomic molecules , 1981 .

[5]  M. Gordon,et al.  Expansion approach to photodissociation dynamics. Effect of anharmonicity , 1981 .

[6]  J. Simons,et al.  Energy partitioning in photodissociation: state selective studies of the cyanogen halides , 1981 .

[7]  J. Light,et al.  Photodissociation of triatomic molecules: Application of the R‐matrix propagation methods to the calculation of bound‐free Franck–Condon factors , 1980 .

[8]  W. Gelbart,et al.  Bending contribution to rotational distributions in the photodissociation of polyatomic molecules , 1980 .

[9]  M. Shapiro,et al.  Resonances in the H2O photodissociation: A converged three‐dimensional quantum mechanical study , 1980 .

[10]  G. A. Parker,et al.  A variable interval variable step method for the solution of linear second order coupled differential equations , 1980 .

[11]  K. Freed,et al.  Rotational distributions in photodissociation: the bent triatomic molecule , 1980 .

[12]  J. Simons,et al.  Photodissociation spectroscopy of the cyanogen halides in the vacuum ultraviolet , 1980 .

[13]  J. Gouyet,et al.  SCF CI calculation on HCN: HCN dissociation curves , 1979 .

[14]  K. Freed,et al.  Rotational distributions from photodissociation. II. Results for ICN+hν→l+CN(X 2Σ+) , 1979 .

[15]  J. Gouyet,et al.  SCF CI calculations on HCN excited states , 1978 .

[16]  E. Heller.  Photofragmentation of symmetric triatomic molecules: Time dependent picture , 1978 .

[17]  J. Simons,et al.  The dynamics of photodissociation of HCN and DCN; theoretical predictions and experimental observations , 1978 .

[18]  K. Freed,et al.  Comparison of semiclassical treatments for evaluating Franck–Condon transition amplitudes for molecular dissociation , 1978 .

[19]  E. Heller.  Quantum corrections to classical photodissociation models , 1978 .

[20]  K. Freed,et al.  Design of natural collision coordinates to describe dissociation of polyatomic molecules , 1978 .

[21]  J. Simons,et al.  Spectroscopic study of the predissociation H(D)CN(C1A′)→ H(D)+ CN(B2Σ+) , 1978 .

[22]  O. Atabek,et al.  Coupled equations applied to the photodissociation of linear triatomics: A test of approximate schemes for calculating the line shape and the effect of final states interactions , 1977 .

[23]  M. Shapiro,et al.  Theory of the A-system photodissociation of ICN , 1977 .

[24]  M. Shapiro.  Exact collinear calculations of the N2 O(X1∑+) → N2(1∑+g) + O(1S) photodissociation process , 1977 .

[25]  G. Schatz,et al.  Quantum mechanical reactive scattering for three-dimensional atom plus diatom systems. I. Theory , 1976 .

[26]  S. Mukamel,et al.  Photofragmentation of linear triatomics , 1976 .

[27]  K. Freed,et al.  Distribution of vibrational populations of CO electronic states produced in CO2 photodissociation , 1976 .

[28]  K. Freed,et al.  Large isotope effects in photodissociation of polyatomic molecules , 1975 .

[29]  K. Freed,et al.  Dissociation processes of polyatomic molecules , 1975 .

[30]  K. Freed,et al.  Quantum theory of photodissociation of polyatomic molecules: Application to HCN , 1974 .

[31]  G. Schwenzer,et al.  Geometries of the excited electronic states of HCN , 1974 .

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

[33]  M. Shapiro.  Photodissociation and Half‐Collisions — Computational Viewpoint and Boundary Conditions , 1973 .

[34]  S. Flügge,et al.  Practical Quantum Mechanics , 1976 .

[35]  R. Bernstein,et al.  Classical Study of Rotational Excitation of a Rigid Rotor: Li+ + H2 , 1971 .

[36]  M. E. Rose,et al.  Elementary Theory of Angular Momentum , 1957 .

[37]  G. Herzberg,et al.  Infrared and Raman spectra of polyatomic molecules , 1946 .