Theoretical transition probabilities for the OH Meinel system

Abstract An electric dipole moment function (EDMF) for the X 2 Π ground state of OH based on the complete-active-space self-consistent-field plus multi-reference-singles-plus-double-excitation configuration-interaction procedure using an extended Slater basis is reported. This EDMF and the recently published MCSCF(7)-self-consistent electron pairs (SCEP) EDMF of H-J. Werner, P. Rosmus, and E-A. Reinsch [ J. Chem. Phys. 79 , 905–916 (1983)] (WRR) are critically compared with the “experimentally” derived EDMF. Einstein coefficients calculated with both theoretical EDMFs are substantially different than those reported by F. H. Mies [ J. Mol. Spectrosc. 53 , 150–188 (1974)] based on the EDMF of W. J. Stevens, G. Das, A. C. Wahl, D. Neumann, and M. Krauss [ J. Chem. Phys. 61 , 3686–3699 (1974)]. By shifting the WRR EDMF by 0.03 Bohr to larger r , it is possible to reproduce the accurate experimental value for the difference in dipole moments between the v = 0 and v = 1 levels measured using the molecular beam electric resonance technique. Following the theory of Mies (except that Hill and Van Vleck's intermediate coupling approximation is used), revised Einstein coefficients are tabulated for Δ v = v ′ – v ″ ranging from the fundamental transition, Δ v = 1 to the Δ v = 5 overtone for v ′ = 1–9, and J ′ = 0.5–15.5 using the “shifted” WRR EDMF. Theoretical emission spectra are also presented, and the potential for OH involvement in the surface glow of space vehicles is briefly discussed.

[1]  S. Langhoff,et al.  Radiative lifetimes and dipole moments of the A 2Σ+, B 2Σ+, and C 2Σ+ states of OH , 1982 .

[2]  T. Slanger.  Conjectures on the origin of the surface glow of space vehicles , 1983 .

[3]  R. E. Murphy.  Infrared Emission of OH in the Fundamental and First Overtone Bands , 1971 .

[4]  B. Roos,et al.  The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule , 1981 .

[5]  V. I. Krassovsky,et al.  On the OH airglow , 1961 .

[6]  F. Mies.  Calculated vibrational transition probabilities of OH(X2Π) , 1974 .

[7]  S. Langhoff,et al.  Theoretical study of the spin-orbit coupling in the X2? state of OH , 1982 .

[8]  B. Robinson,et al.  OH Molecules in the Interstellar Medium , 1967 .

[9]  H. Werner,et al.  Molecular properties from MCSCF‐SCEP wave functions. I. Accurate dipole moment functions of OH, OH−, and OH+ , 1983 .

[10]  Alexander Dalgarno,et al.  The surface glow of the Atmosphere Explorer C and E satellites , 1983 .

[11]  S. Langhoff,et al.  Theoretical study of the Λ-doubling parameters for X2Π OH , 1984 .

[12]  Pavel Rosmus,et al.  PNO–CI and CEPA studies of electron correlation effects. III. Spectroscopic constants and dipole moment functions for the ground states of the first‐row and second‐row diatomic hydrides , 1975 .

[13]  E. L. Hill,et al.  On the Quantum Mechanics of the Rotational Distortion of Multiplets in Molecular Spectra , 1928 .

[14]  D. Garvin.  Chemically Induced Vibrational Excitation: A Study of Hydroxyl Radicals Formed in the H + O3Atomic Flame1,2 , 1959 .

[15]  Claus Ehrhardt,et al.  The coupled pair functional (CPF). A size consistent modification of the CI(SD) based on an energy functional , 1985 .

[16]  E. F. Dishoeck,et al.  An analysis of vibration-rotation lines of OH in the solar infrared spectrum , 1984 .

[17]  M. Yoshimine,et al.  Ab initio study of the X2Π and A2Σ+ states of OH. I. Potential curves and properties , 1974 .

[18]  J. A. Coxon,et al.  Rotational analysis of hydroxyl vibration–rotation emission bands: Molecular constants for OH X2Π, 6 ≤ ν ≤ 10 , 1982 .

[19]  Wilfried Meyer,et al.  PNO-CI and CEPA studies of electron correlation effects , 1974 .

[20]  W. J. Stevens,et al.  Study of the ground state potential curve and dipole moment of OH by the method of optimized valence configurations , 1974 .

[21]  D. Lambert,et al.  Astronomical Infrared Spectroscopy with a Connes-Type Interferometer. III. Alpha Orionis, 2600-3450 CM^{-1}. , 1972 .

[22]  H. J. Kostkowski,et al.  Chemically Induced Vibrational Excitation: Hydroxyl Radical Emission in the 1–3 Micron Region Produced by the H+O3 Atomic Flame , 1960 .

[23]  A. F. Ferguson,et al.  THE HYDROXYL BANDS IN THE NIGHTGLOW , 1963 .

[24]  J. A. Coxon,et al.  Radial dependence of spin-orbit and Λ-doubling parameters in the X2Π ground state of hydroxyl , 1982 .

[25]  H. R. Johnson,et al.  Carbon, nitrogen and oxygem abundances in Betelgeuse. , 1984 .

[26]  G. Stokes,et al.  The pure rotation spectrum of OH and the solar oxygen abundance , 1984 .

[27]  I. Meinel,et al.  OH Emission Bands in the Spectrum of the Night Sky. , 1950 .

[28]  G. T. Fraser,et al.  Electric dipole moment of X2Π OH and OD in several vibrational states , 1984 .