DYNAMIC COUPLING PHENOMENA IN MOLECULAR EXCITED STATES. III. ASSOCIATIVE IONIZATION AND DISSOCIATIVE RECOMBINATION IN H .

A detailed calculation based on a perturbed stationary-state description is presented for associative ionization of hydrogen atoms. Specific rate constants ${k}_{\mathrm{AI}} (v,K,T)$ are evaluated for the set of electronic states correlating with $\mathrm{H}(n=1)+\mathrm{H}(n=3)$ for associative ionization into vibrational ($v=0\ensuremath{-}8$) and rotational ($K=0\ensuremath{-}21$) states of $\mathrm{H}_{2}^{}{}_{}{}^{+}({X}^{2}{\ensuremath{\Sigma}}_{g}^{+})$ at $T=300$ \ifmmode^\circ\else\textdegree\fi{}K and at $T=600$ \ifmmode^\circ\else\textdegree\fi{}K. Cross sections ${Q}_{\mathrm{AI}}(v,K,E)$ are given for the most significant electronic state, the ($1s\ensuremath{\sigma},4s\ensuremath{\sigma}$) united atom configuration, and, by microscopic reversibility, cross sections for the reverse reaction, dissociative recombination, are obtained. Cross sections for associative ionization at thermal energies, ${Q}_{\mathrm{AI}}(v,K,{10}^{\ensuremath{-}3}\mathrm{a}.\mathrm{u}.)$, are at most of a magnitude about ${10}^{\ensuremath{-}18}$ ${\mathrm{cm}}^{2}$. Corresponding specific rate constants, ${k}_{\mathrm{AI}}$ ($v,K,300$ \ifmmode^\circ\else\textdegree\fi{}K), fall in the range ${10}^{\ensuremath{-}14}$-${10}^{\ensuremath{-}13}$ ${\mathrm{cm}}^{3}$/sec and display a temperature dependence ${k}_{\mathrm{AI}}(T)\ensuremath{\propto}{T}^{\ensuremath{-}0.33}$. Dissociative recombination cross sections, ${Q}_{\mathrm{DR}}(v,K,{10}^{\ensuremath{-}3}\mathrm{a}.\mathrm{u}.)$, are obtained for the $v=4\ensuremath{-}8$ vibrational states, with magnitudes about ${10}^{\ensuremath{-}16}$ ${\mathrm{cm}}^{2}$. The resulting specific rate constants, ${k}_{\mathrm{Dr}}$ ($v,K,300$ \ifmmode^\circ\else\textdegree\fi{}K), are at most ${10}^{\ensuremath{-}10}$ ${\mathrm{cm}}^{3}$/sec and display a temperature dependence ${k}_{\mathrm{DR}}({T}_{e})\ensuremath{\propto}T_{e}^{}{}_{}{}^{\frac{\ensuremath{-}1}{2}}$ for ${T}_{e}\ensuremath{\lesssim}80$ \ifmmode^\circ\else\textdegree\fi{}K, ${k}_{\mathrm{DR}}({T}_{e})\ensuremath{\propto}T_{e}^{}{}_{}{}^{\ensuremath{-}0.75}$ for ${T}_{e}\ensuremath{\approx}300$ \ifmmode^\circ\else\textdegree\fi{}K, and a still larger-power decrease for increasing ${T}_{e}$ at ${T}_{e}g300$ \ifmmode^\circ\else\textdegree\fi{}K.

[1]  R. Berry,et al.  Dynamic Coupling Phenomena in Molecular Excited States. II. Autoionization and Predissociation in H 2 , Hd, and D 2 , 1970 .

[2]  R. Berry,et al.  DYNAMIC COUPLING PHENOMENA IN MOLECULAR EXCITED STATES. I. GENERAL FORMULATION AND VIBRONIC COUPLING H . , 1970 .

[3]  R. Berry.  Electronic Spectroscopy by Electron Spectroscopy , 1969 .

[4]  T. F. O'Malley.  Theory of Dissociative Recombination in Vibrationally Excited Gases , 1969 .

[5]  W. Kołos,et al.  Theoretical Investigation of the Lowest Double‐Minimum State E, F 1Σg+ of the Hydrogen Molecule , 1969 .

[6]  M. Mittleman,et al.  FORMAL PROBLEMS IN THE THEORY OF DISSOCIATIVE ATTACHMENT AND RECOMBINATION. , 1968 .

[7]  W. Kołos.  Recent developments in the theory of one- and two-electron molecules† , 1968 .

[8]  W. Kołos,et al.  Vibrational and Rotational Energies for the B 1Σu + , C 1Πu, and a 3Σg + States of the Hydrogen Molecule , 1968 .

[9]  J. Peacher,et al.  Associative Detachment: H+H - -->H 2 * +e , 1968 .

[10]  M. A. Biondi,et al.  Electron-Temperature Dependence of Electron-Ion Recombination in Argon , 1968 .

[11]  G. Born.  RECOMBINATION OF ELECTRONS AND MOLECULAR HELIUM IONS. , 1968 .

[12]  M. Russell,et al.  Ion‐Molecule and Chemi‐ionization Reactions in H2 by Photoionization , 1968 .

[13]  F. T. Chan.  Electron-Ion and Ion-Ion Dissociative Recombination of Oxygen. , 1968 .

[14]  J. Bardsley.  The ionization of molecules near threshold , 1967 .

[15]  J. Peek.  Theory of Dissociation of H 2 + by Fast Electrons , 1967 .

[16]  G. Dunn,et al.  Electron Impact Dissociation of H+2 , 1967 .

[17]  S. Nielsen,et al.  Theory of the Dissociative Recombination and Associative Ionization of Hydrogen , 1966 .

[18]  L. Wolniewicz,et al.  Potential‐Energy Curve for the B1Σu+ State of the Hydrogen Molecule , 1966 .

[19]  W. W. Robertson,et al.  Hornbeck—Molnar Cross Sections for the n=3 States of Helium , 1966 .

[20]  C. Warke.  Nonradiative Dissociative Electron Capture by Molecular Ions , 1966 .

[21]  R. Wilkins.  Monte Carlo Calculations of Cross Sections of Electron—Positive‐Molecular‐Ion Dissociative Recombination , 1966 .

[22]  C. Collins.  Collisional-dissociative recombination of electrons with molecular ions. , 1965 .

[23]  W. W. Robertson,et al.  Comments on Collisional—Radiative Recombination of He2+ into Dissociative States , 1965 .

[24]  F. W. Lampe,et al.  Mass‐Spectrometric Study of the Bimolecular Formation of Diatomic Argon Ion , 1965 .

[25]  F. Fehsenfeld,et al.  Dissociative Recombination in Helium Afterglows , 1965 .

[26]  W. W. Robertson.  Collisional-Radiative Recombination of He+2 into Dissociative States , 1965 .

[27]  R. S. Mulliken.  RARE-GAS AND HYDROGEN MOLECULE ELECTRONIC STATES, NONCROSSING RULE, AND RECOMBINATION OF ELECTRONS WITH RARE-GAS AND HYDROGEN IONS , 1964 .

[28]  H. J. Oskam,et al.  RECOMBINATION COEFFICIENT OF MOLECULAR RARE-GAS IONS , 1963 .

[29]  R. Curran.  Mass‐Spectrometer Investigation of Electron‐Impact Processes at Pressures to 1 mm Hg , 1963 .

[30]  R. Taubert,et al.  Notizen: Die Lebensdauer der angeregten Reaktanten in Neutralreaktionen (I) , 1963 .

[31]  D. R. Bates,et al.  Recombination between electrons and atomic ions, I. Optically thin plasmas , 1962, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[32]  F. H. Field,et al.  Rare‐Gas Molecule‐Ion Formation by Mass Spectrometry. Kinetics of Ar2+, Ne2+, and He2+ Formation by Second‐ and Third‐Order Processes , 1962 .

[33]  L. Goldstein,et al.  ELECTRON TEMPERATURE DEPENDENCE OF THE RECOMBINATION COEFFICIENT IN PURE HELIUM , 1961 .

[34]  S. Brown,et al.  Electron Loss Process in the Hydrogen Afterglow , 1955 .

[35]  J. P. Molnar,et al.  MASS SPECTROMETRIC STUDIES OF MOLECULAR IONS IN THE NOBLE GASES , 1951 .

[36]  D. R. Bates.  Electron Recombination in Helium , 1950 .

[37]  E. Wigner.  On the Behavior of Cross Sections Near Thresholds , 1948 .