MOLECULAR SPECTROSCOPY OF PLANETARY ATMOSPHERES
Molecular spectroscopy of planetary atmospheres - venus and mars
PLANETARY ATMOSPHERE↗
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Molecular spectroscopy and planetary exploration from space
Examples of the role which molecular spectroscopy played in the interpretation of the thermal emission spectra of Earth, Mars, and Jupiter are given. Some advantages of molecular spectroscopy from a spacecraft passing close to a planet, or from an orbiter, over ground based techniques are discussed. Specifically the possibility of obtaining spectra over a wide spectral range (1) without the obscuring effect of Earth's atmosphere, (2) at much higher spatial resolution, and (3) from directions and with phase angles inaccessible from Earth.
Hanel, R.↗
Molecular Spectroscopy in Astrophysics: The Case of Polycyclic Aromatic Hydrocarbons
The role of molecular spectroscopy in astrophysics and astrochemistry is discussed in the context of the study of large, complex, carbon-bearing molecules, namely, Polycyclic Aromatic Hydrocarbons or PAHs. These molecular species are now thought to be widespread in the interstellar medium in their neutral and ionized forms. Identifying the carriers responsible for unidentified interstellar spectral bands will allow to derive important information on cosmic elemental abundances as well as information on the physical conditions (density, temperature) reigning in specific interstellar environments. These, in turn, are key elements for a correct understanding of the energetic mechanisms that govern the origin and the evolution of the interstellar medium. A multidisciplinary approach - combining astronomical observations with laboratory simulations and theoretical modeling - is required to address these complex issues. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices or seeded in a supersonic jet expansion, are discussed here and compared to the astronomical spectra of reddened, early type, stars. The electronic spectroscopy of PAHs in the ultraviolet, visible, and near-infrared domains is reviewed and an assessment of the potential contribution of PAHs to the interstellar extinction in the ultraviolet and in the visible is discussed.
Salama, Farid↗
Molecular spectroscopy and collisional excitation
The paper examines the basic principles underlying the molecular transitions responsible for interstellar molecular spectra. The energy levels of molecules are discussed in detail with special attention given to the Born-Oppenheimer approximation, the electronic Hamiltonian, and the parameters of vibrational and rotational energy. The probabilities for radiative and collisional transitions are calculated. A brief review of techniques for molecular spectroscopy is presented along with methods used to determine collision cross sections on both an experimental and a theoretical basis.
Green, S.↗
Molecular Spectroscopy in Astrophysics: Interstellar PAHs
Polycyclic aromatic hydrocarbons (PAHs) are now considered to be an important and ubiquitous component of the organic material in space. PAHs are found in a large variety of extraterrestrial materials such as interplanetary dust particles (IDPs) and meteoritic materials. PAHs are also good candidates to account for the infrared emission bands (UIRs) and the diffuse interstellar optical absorption bands (DIBs) detected in various regions of the interstellar medium. The recent observations made with the Infrared Space Observatory (ISO) have confirmed the ubiquitous nature of the UIR bands and their carriers. PAHs are thought to form through chemical reactions in the outflow from carbon-rich stars in a process similar to soot formation. Once injected in the interstellar medium, PAHs are further processed by the interstellar radiation field, interstellar shocks and energetic particles. A long-term laboratory effort has been undertaken to measure the physical and chemical characteristics of these carbon molecules and their ions under experimental conditions that mimic the interstellar conditions. These measurements require collision-free conditions where the molecules and ions are cold and chemically isolated. The spectroscopy of PAHs under controlled conditions represents an essential diagnostic tool to study the evolution of extraterrestrial PAHs. The laboratory results will be discussed as well as the implications for astronomy and for molecular spectroscopy. A review of the data generated through laboratory simulations of space environments and the role these data have played in our current understanding of the properties of interstellar PAHs will be presented. We will also present the new generation of laboratory experiments that are currently being developed in order to provide a closer simulation of space environments and a better support to space missions.
Salama, Farid↗
MOLECULAR SPECTROSCOPY OF PLANETARY ATMOSPHERES
Study of molecular constituents of planetary atmospheres using various spectroscopic instruments
PLANETARY ATMOSPHERE↗
The application of ab initio calculations to molecular spectroscopy
The state of the art in ab initio molecular structure calculations is reviewed with an emphasis on recent developments, such as full configuration-interaction benchmark calculations and atomic natural orbital basis sets. It is found that new developments in methodology, combined with improvements in computer hardware, are leading to unprecedented accuracy in solving problems in spectroscopy.
Bauschlicher, Charles W., Jr.↗
The application of ab initio calculations to molecular spectroscopy
The state of the art in ab initio molecular structure calculations is reviewed, with an emphasis on recent developments such as full configuration-interaction benchmark calculations and atomic natural orbital basis sets. It is shown that new developments in methodology combined with improvements in computer hardware are leading to unprecedented accuracy in solving problems in spectroscopy.
Bauschlicher, Charles W., Jr.↗
The study of molecular spectroscopy by ab initio methods
This review illustrates the potential of theory for solving spectroscopic problems. The accuracy of approximate techniques for including electron correlation have been calibrated by comparison with full configuration-interaction calculations. Examples of the application of ab initio calculations to vibrational, rotational, and electronic spectroscopy are given. It is shown that the state-averaged, complete active space self-consistent field, multireference configuration-interaction procedure provides a good approach for treating several electronic states accurately in a common molecular orbital basis.
Bauschlicher, Charles W., Jr.↗
Molecular spectroscopy from the Kuiper Airborne Observatory
Interstellar and circumstellar molecules are investigated through medium-resolution infrared spectrosocpy of the vibration-rotation and pure rotational transitions. A primary goal was the construction and improvement of instrumentation for the near and middle infrared regions, wavelengths between 2 and 10 microns. The main instrument was a cooled grating spectrometer with an interchangeable detector focal plane which could be used on the Kuiper Airborne Observatory (KAO) for airborne observations, and also at ground-based facilities. Interstellar shock waves were investigated by H2 emission from the Orion Nebula, W51, and the proto-planetary nebulae CRL 2688 and CRL 618. The observations determined the physical conditions in shocked molecular gas near these objects. From these it was possible to characterize the energetic history of mass loss from both pre- and post-main sequence stars in the regions.
Beckwith, S.↗
Laboratory molecular spectroscopy
The precision required in making spectroscopic measurements is discussed. Remarks are directed specifically to vibration-rotation spectra rather than continuum absorptions. The ultimate precision that is required for line positions is related to the width of the lines which may be no narrower than the Doppler width. The spectroscopic methods considered are those which are of the most general value to the astronomers; those which acquire and can handle large volumes of spectra in digital form, or in a form which is compatible with computer analysis, and in a form which is at least internally consistent. The use of dye laser, grating instruments, and the most versatile instrument for laboratory spectroscopy, the Fourier transform spectrometer is discussed.
Margolis, J.↗
A review of acetylene, ethylene and ethane molecular spectroscopy for planetary applications
Spectroscopic work in acetylene, ethylene and ethane, are of particular interest since the Voyager IRIS observations of Jupiter. Acetylene and ethane but not ethylene were observed in the Jovian spectrum. Two fundamental bands of the observed gases are used to determine the spatial distribution of these hydrocarbons on Jupiter and to illuminate the photochemistry of these species. The 100 to 1000 cm region is discussed and selected examples of current laboratory work are given.
Maguire, W. C.↗
Molecular Spectroscopy by Ab Initio Methods
Due to recent advances in methods and computers, the accuracy of ab calculations has reached a point where these methods can be used to provide accurate spectroscopic constants for small molecules; this will be illustrated with several examples. We will show how ab initio calculations where used to identify the Hermann infrared system in N2 and two band systems in CO. The identification of all three of these band systems relied on very accurate calculations of quintet states. The analysis of the infrared spectra of cool stars requires knowledge of the intensity of vibrational transitions in SiO for high nu and J levels. While experiment can supply very accurate dipole moments for nu = 0 to 3, this is insufficient to construct a global dipole moment function. We show how theory, combined by the experiment, can be used to generate the line intensities up to nu = 40 and J = 250. The spectroscopy of transition metal containing systems is very difficult for both theory and experiment. We will discuss the identification of the ground state of Ti2 and the spectroscopy of AlCu as examples of how theory can contribute to the understanding of these complex systems.
Bauschlicher, Charles W., Jr.↗
Summary of workshop on molecular spectroscopy for atmospheric sensing
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spectroscopy atmosphere↗
Molecular velocimetry using stimulated Raman spectroscopy
Molecular flow velocity of N2 was measured in a supersonic wind tunnel using inverse Raman spectroscopy. This technique employs the large Doppler shift exhibited by the molecules when the pump and probe laser beams are counter-propagating (backward scattering). A retrometer system is employed to yield a vibration-free optical configuration which has the additional advantage of obtaining both the forward and backward scattered spectra simultaneously. The linebreadths and their relative Doppler shift can be used to determine the static pressure, translational temperature, and molecular flow velocity. A demonstration of the concept was performed in a supersonic wind tunnel and included: (1) measurements over the Mach number range 2.50 to 4.63; (2) static pressure measurements (at Mach 2.50) corresponding to a Reynolds number per foot range of 1 to 5 x 10 to the 6th power; and (3) measurements behind the shock wave of a flat plate model.
Exton, R. J.↗