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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 82 (1985), S. 342-352 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rydberg states (1,3Σg+, 1,3Σu+, 1,3Πg, and 1,3Πu) of N2 that converge to the N2+ (X 2Σg+) ion have been calculated. The core orbitals are taken as those of the free N2+(X 2Σg+) ion. The Rydberg electron wave functions are expanded by one-center basis functions which are solution of an electron moving in a sphericalized potential of the N2+(X 2Σg+) ion. This expansion converges rapidly since the basis functions are already a fairly good representation of the Rydberg states especially for the higher ones. The use of one-center expansion allows us to examine the mixing of the basis functions of different angular-momentum quantum number l in the Rydberg states which is found to be generally small. Energy levels are reported for singlet and triplet Rydberg states of the Σ and Π types (Λ=0,1) with l from 0–9 and n through 11. The Rydberg levels with l≥4 are entirely hydrogenic. For lower l the quantum defect varies significantly with n within a given l series. Also a wide range of quantum defect is found for different states. Transitions among the various Rydberg series produce a very rich spectrum in the long-wave infrared region.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 1261-1275 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Coriolis-induced vibrational mixing in S1 H2CO near Evib =2000–2300 cm−1 is manifested by the rotational quantum number (J′,K′a) dependent variation of the emission intensity in the rotationally resolved, dispersed fluorescence spectrum. The c-axis Coriolis resonance between 2143 (Ka=5) and 214161 (K′a=4) is observed with ξ(c)st (approximately-equal-to)0.2 cm−1. The b-axis Coriolis interaction between 214161 (Ka=5) and 4461 (K′a=4) in S1 as well as the a-axis Coriolis interaction between 42 and 4161 in S0 are observed. A significant degree of vibrational mixing is observed in the energy range, Evib =2000–2300 cm−1.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 6991-6994 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: FTIR spectra of the matrix-isolated monomeric and complexed H2S in solid O2 at 13 K have been obtained at various matrix: solute ratios (M/S) in order to identify the ν3 absorption of the monomer. The ν1 absorption of the monomer was too weak to be seen at high dilutions, M/S∼4000 and 8000. The previous assignments of the monomer ν1 absorption in Ar and N2 are questioned. The satellite peaks appearing at low values of (M/S) are assigned to (H2S)2. The observed H-bonding dimer frequency, −50 cm−1 from v3, is comparable to the value calculated using second-order Møller-Plesset perturbation theory. Frequencies calculated at the Hartree–Fock level for H2S dimer are essentially unchanged from those in the monomer.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 1039-1040 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: SRL lifetimes of the jet-cooled S1 H2CO molecules with low J' and K' values have been studied for the excitation of v'4=1 and 3, v5=1, and v'6=1. The v4 excitation leads to considerably faster S1 u S0 radiationless decay than the v'5 and v6 excitation, showing the vibrational mode specificity and correlation predicted by the molecular dissociation theory.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 5290-5302 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of Coriolis coupling on intensities in infrared rotation–vibration bands is here extended to vibronically allowed transitions between electronic states of a nearly symmetric top. Within the framework of the Herzberg–Teller treatment of vibronic interaction, equations are developed which describe the intensity distribution in the p- and r-form branches of a vibronic transition in the cases where Coriolis interaction perturbs one or both vibrational levels associated with the transition. The A˜ 1A2–X˜ 1A1 transition in H2CO is used as an example to illustrate the theory.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 28-44 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: It has been found in the rotationally resolved fluorescence emission of the 51 and 1141 levels of S1 H2CO that the rotational line intensity distributions of various vibronic bands are very unusual. This is due to the Coriolis interaction between the zero-order 51 and 1141 rotational levels and also the interaction between these and other neighboring levels. The theory of the rotational intensity bias and borrowing based on the rotation-induced vibrational mixing is used to explain the intensity anomaly as well as the variation in the mixing coefficients with the variation in the rotational quantum numbers, J' and Ka. For most of the rotational levels populated at room temperature, the Coriolis-induced vibrational mixing of 51 and 1141 appears nearly complete.
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