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  • 1
    Publication Date: 1996-06-22
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 2
    Publication Date: 1995-02-15
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 3
    Publication Date: 1998-03-01
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 4
    Publication Date: 1999-10-01
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 5
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    In:  CASI
    Publication Date: 2004-12-03
    Description: The theoretical modeling of atmospheric spectra is important for a number of different applications: for instance, in the determination of minor atmospheric constituents such as ozone, carbon dioxide, CFC's etc.; in monitoring the temperature profile for climate studies; and in measuring the incoming and outgoing radiation to input into global climate models. In order to accomplish the above mentioned goal, one needs to know the spectral parameters characterizing the individual spectral lines (frequency, width, strength, and shape) as well as the physical parameters of the atmosphere (temperature, abundances, and pressure). When all these parameters are known, it is usually assumed that the resultant spectra and concomitant absorption coefficient can then be calculated by a superposition of individual profiles of appropriate frequency, strength and shape. However, this is not true if the lines are 'coupled'. Line coupling is a subtle effect that takes place when lines of a particular molecule overlap in frequency. In this case when the initial states and the final states of two transitions are connected by collisions, there is a quantum interference resulting in perturbed shapes. In general, this results in the narrowing of Q-branches (those in which the rotational quantum number does not change), and vibration-rotational R- and P branches (those in which the rotational quantum number changes by +/- 1), and in the spectral region beyond band heads (regions where the spectral lines pile up due to centrifugal distortion). Because these features and spectral regions are often those of interest in the determination of the abundances and pressure-temperature profiles, one must take this effect into account in atmospheric models.
    Keywords: Geophysics
    Format: text
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  • 6
    Publication Date: 2019-06-28
    Description: A far-wing line shape theory based on the binary collision and quasistatic approximations that is applicable for both the low- and high-frequency wings of allowed vibrational-rotational lines has been developed. This theory has been applied in order to calculate the frequency and temperature dependence of the continuous absorption coefficient for frequencies up to 10,000 cm(exp -1) for pure H2O and for H2O-N2 mixtures. The calculations are made assuming an interaction potential consisting of an isotropic Lennard-Jones part and the leading long-range anisotropic part, and utilizing the measured line strengths and transition frequencies. The results compare well with existing data, both in magnitude and in temperature dependence. This leads us to the conclusion that although dimer and collision-induced absorptions are present, the primary mechanism responsible for the observed water continuum is the far-wing absorption of allowed lines. Recent progress on near-wing corrections to the theory and validations with recent laboratory measurements are discussed briefly.
    Keywords: COMMUNICATIONS AND RADAR
    Type: NASA-CR-199516 , NAS 1.26:199516
    Format: application/pdf
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  • 7
    Publication Date: 2019-06-28
    Description: A far-wing theory in which the validity of the detailed balance principle is maintained in each step of the derivation is presented. The role of the total density matrix including the initial correlations is analyzed rigorously. By factoring out the rapidly varying terms in the complex-time development operator in the interaction representation, better approximate expressions can be obtained. As a result, the spectral density can be expressed in terms of the line-coupling functions in which two coupled lines are arranged symmetrically and whose frequency detunings are omega - 1/2(omega(sub ji) + omega (sub j'i'). Using the approximate values omega - omega(sub ji) results in expressions that do not satisfy the detailed balance principle. However, this principle remains satisfied for the symmetrized spectral density in which not only the coupled lines are arranged symmetrically, but also the initial and final states belonging to the same lines are arranged symmetrically as well.
    Keywords: AERODYNAMICS
    Type: NASA-TM-111075 , NAS 1.15:111075
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  • 8
    Publication Date: 2019-07-10
    Description: The far-wing line shape theory within the binary collision and quasistatic framework has been developed using the coordinate representation. Within this formalism, the main computational task is the evaluation of multidimensional integrals whose variables are the orientational angles needed to specify the initial and final positions of the system during transition processes. Using standard methods, one is able to evaluate the 7-dimensional integrations required for linear molecular systems, or the 7-dimensional integrations for more complicated asymmetric-top (or symmetric-top) molecular systems whose interaction potential contains cyclic coordinates. In order to obviate this latter restriction on the form of the interaction potential, a Monte Carlo method is used to evaluate the 9-dimensional integrations required for systems consisting of one asymmetric-top (or symmetric-top) and one linear molecule, such as H20-N2. Combined with techniques developed previously to deal with sophisticated potential models, one is able to implement realistic potentials for these systems and derive accurate, converged results for the far-wing line shapes and the corresponding absorption coefficients. Conversely, comparison of the far-wing absorption with experimental data can serve as a sensitive diagnostic tool in order to obtain detailed information on the short-range anisotropic dependence of interaction potentials.
    Keywords: Atomic and Molecular Physics
    Type: GCN-99-61
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 3009-3010 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Comparisons are made between different methods of introducing the principle of detailed balance in far-wing line shape theories. In particular, it is shown that by symmetrizing the operators in the quasistatic formulation of Ma and Tipping [J. Chem. Phys. 95, 6290 (1991)], one can obtain the same results for the symmetrized matrix elements of the relaxation operator and their frequency detuning that were introduced in an ad hoc way in the resonant quasistatic formulations of Boulet and co-workers [J. Chem. Phys. 91, 2163 (1989); 94, 6406 (1991)]. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 9678-9688 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We develop the basic formalism of a far-wing line shape theory that satisfies the detailed balance principle. For molecular systems of interest, e.g., CO2–Ar at room temperature or higher, there are many individual vibration–rotational lines in a given band and many bands in the spectrum. In such cases, one must make additional approximations in order to carry out accurate calculations of the absorption coefficient using a reasonable amount of computer time. In the present paper, we discuss two such simplifications: the frequency detuning approximation of the line-coupling functions and the band-average approximation. We then apply the theory to a calculation of the far-wing absorption of the ν3 band of CO2 perturbed by Ar, successively including the effects of more lines in the calculations by increasing Jmax from 40 to 108. From the results of this work, we find that the frequency detuning approximation is good only for frequencies of interest far from the band center. In addition, we find that contrary to previous assertions of the adequacy of the first-order band-average approximation, the higher-order terms are significant. To a good approximation these can be incorporated by introducing a frequency shift in the first-order results so that extensive additional calculations are not required. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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