Molecular polymorphism: microwave spectra, equilibrium structures, and an astronomical investigation of the HNCS isomeric family
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Brett A. McGuire↗
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The Effects of Low- and High-Energy Cutoffs on Solar Flare Microwave and Hard X-Ray Spectra
Microwave and hard x-ray spectra provide crucial information about energetic electrons and their environment in solar flares. These spectra are becoming better determined with the Owens Valley Solar Array (OVSA) and the recent launch of the Ramaty High Energy Solar Spectroscopic Imager (RHESSI). The proposed Frequency Agile Solar Radiotelescope (FASR) promises even greater advances in radio observations of solar flares. Both microwave and hard x-ray spectra are sensitive to cutoffs in the electron distribution function. The determination of the high-energy cutoff from these spectra establishes the highest electron energies produced by the acceleration mechanism, while determination of the low-energy cutoff is crucial to establishing the total energy in accelerated electrons. This paper will show computations of the effects of both high- and low-energy cutoffs on microwave and hard x-ray spectra. The optically thick portion of a microwave spectrum is enhanced and smoothed by a low-energy cutoff, while a hard x-ray spectrum is flattened below the cutoff energy. A high-energy cutoff steepens the microwave spectrum and increases the wavelength at which the spectrum peaks, while the hard x-ray spectrum begins to steepen at photon energies roughly an order of magnitude below the electron cutoff energy. This work discusses how flare microwave and hard x-ray spectra can be analyzed together to determine these electron cutoff energies. This work is supported in part by the NASA Sun-Earth Connection Program.
Holman, G. D.↗
Great microwave bursts and hard X-rays from solar flares
The microwave and hard X-ray charateristics of 13 solar flares that produced microwave fluxes greater than 500 Solar Flux Units were analyzed. These Great Microwave Bursts were observed in the frequency range from 3 to 35 GHz at Berne, and simultaneous hard X-ray observations were made in the energy range from 30 to 500 keV with the Hard X-Ray Burst Spectrometer on the Solar Maximum Mission spacecraft. The principal aim of this analysis is to determine whether or not the same distribution of energetic electrons can explain both emissions. Correlations were found between respective temporal characteristics and, for the first time, between microwave and hard X-ray spectral characteristics. A single-temperature and a multi-temperature model from the literature were tested for consistency with the coincident X-ray and microwave spectra at microwave burst maximum. Four events are inconsistent with both of the models tested, and neither of the models attempts to explain the high-frequency part of the microwave spectrum. A model in which the emissions above and below the peak frequency originate in two different parts of a diverging magnetic loop is proposed. With this model the entire microwave spectrum of all but one of the events is explained.
Wiehl, H. J.↗
Great microwave bursts and hard X-rays from solar flares
In the present study of the microwave and hard X-ray characteristics of 13 solar flares emitting microwave fluxes greater than 500 solar flux units, simultaneous 3-35 GHz and hard X-ray observations were conducted in the 30-500 keV energy range. An analysis is conducted to determine whether the same distribution of energetic electrons can explain both emissions; tests for any correlations between them yield results suggesting that optically thick microwave emission, near the peak frequency, originates in the same electron population that produces the hard X-rays. A single temperature model and a multitemperature model were tested for consistency with the coincident X-ray and microwave spectra at microwave burst maximum; neither model, however, attempts to explain the high frequency component of the microwave spectrum.
Wiehl, H. J.↗
Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation
The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH 3 –$CH=CH$–CH 2 –CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C 5 H 7 N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Spectral evolution of microwaves and hard X-rays in the 1989 March 18 flare and its interpretation
We analyze the time variation of microwave spectra and hard X-ray spectra of 1989 March 18, which are obtained from the Solar Array at the Owens Valley Radio Observatory (OVRO) and the Hard X-Ray Burst Spectrometer (HXRBS) on the Solar Maximum Mission (SMM), respectively. From this observation, it is noted that the hard X-ray spectra gradually soften over 50 - 200 keV on-and-after the maximum phase while the microwaves at 1 - 15 GHz show neither a change in spectral shape nor as rapid a decay as hard X-rays. This leads to decoupling of hard X-rays from the microwaves in the decay phase away from their good correlation seen in the initial rise phase. To interpret this observation, we adopt a view that microwave-emitting particles and hard X-ray particles are physically separated in an inhomogeneous magnetic loop, but linked via interactions with the Whistler waves generated during flares. From this viewpoint, it is argued that the observed decoupling of microwaves from hard X-rays may be due to the different ability of each source region to maintain high energy electrons in response to the Whistler waves passing through the entire loop. To demonstrate this possibility, we solve a Fokker-Planck equation that describes evolution of electrons interacting with the Whistler waves, taking into account the variation of Fokker-Planck coefficients with physical quantities of the background medium. The numerical Fokker-Planck solutions are then used to calculate microwave spectra and hard X-ray spectra for agreement with observations. Our model results are as follows: in a sronger field region, the energy loss by electron escape due to scattering by the waves is greatly enhanced resulting in steep particle distributions that reproduce the observed hard X-ray spectra. In a region with weaker fields and lower density, this loss term is reduced allowing high energy electrons to survive longer so that microwaves can be emitted there in excess of hard X-rays during the decay phase of the flare. Our results based on spectral fitting of a flare event are discussed in comparison with previous studies of microwaves and hard X-rays based on either temporal or spatial information.
Lee, Jeongwoo W.↗
Temperature/pressure and water vapor sounding with microwave spectroscopy
Two intense microwave spectra lines exist in the martian atmosphere that allow unique sounding capabilities: water vapor at 183 GHz and the (2-1) rotational line of CO at 230 GHz. Microwave spectra line sounding is a well-developed technique for the Earth's atmosphere for sounding from above from spacecraft and airplanes, and from below from fixed surface sites. Two simple instruments for temperature sounding on Mars (the CO line) and water vapor measurements are described. The surface sounder proposed for the MESUR sites is designed to study the boundary layer water vapor distribution and the temperature/pressure profiles with vertical resolution of 0.25 km up to 1 km with reduced resolution above approaching a scale height. The water channel will be sensitive to a few tenths of a micrometer of water and the temperature profile will be retrieved to an accuracy between 1 and 2 K. The latter is routinely done on the Earth using oxygen lines near 60 GHz. The measurements are done with a single-channel heterodyne receiver looking into a 10-cm mirror that is canned through a range of elevation angles plus a target load. The frequency of the receiver is sweep across the water and CO lines generating the two spectra at about 1-hr intervals throughout the mission. The mass and power for the proposed instrument are 2 kg and 5-8 W continuously. The measurements are completely immune to the atmospheric dust and ice particle loads. It was felt that these measurements are the ultimate ones to properly study the martian boundary layer from the surface to a few kilometers. Sounding from above requires an orbiting spacecraft with multichannel microwave spectrometers such as the instrument proposed for MO by a subset of the authors, a putative MESUR orbiter, and a proposed Discovery mission called MOES. Such an instrument can be built with less than 10 kg and use less than 15 W. The obvious advantage of this approach is that the entire atmosphere can be sounded for temperature and water vapor in a few hours with somewhat better than a scale height resolution. If a bigger mirror is used (greater than 30 cm) limb sounding geometry can be employed and half scale height resolution achieved to altitudes up to at least 60 km. Again, the measurements are immune to dust and ice loads. Water vapor sensitivity of 0.1 micrometer can be achieved (even with a nadir instrument) and temperature profiles retrieved to an accuracy of better than 2 K from the surface to about 60 km. Winds can be measured from the doppler shifts of CO lines in the limb sounding mode.
Muhleman, D. O.↗
Direct electric field heating and acceleration of electrons in solar flares
We show that the observed properties of solar flare X-ray and microwave emission can be explained through the Joule heating and electric field acceleration of runaway electrons in current channels. The global properties of the flaring region required for this are presented. We have fit a hybrid thermal/nonthermal electron distribution, consisting of hot, isothermal electrons with a nonthermal tail of runaway electrons, to high-resolution hard X-ray and microwave spectra and have obtained excellent fits to both. The hybrid model relaxes the electron number and energy flux requirements for the hard X-ray emission over those of a purely nonthermal model. The model also provides explanations for several previously unexplained aspects of the high-resolution microwave spectra. The fit parameters can be related to physical properties (such as the electric field strength in the current channels) of the acceleration region.
Holman, Gordon D.↗
Global changes in the 0-70 km thermal structure of the Mars atmosphere derived from 1975 to 1989 microwave CO spectra
J = 1 - 2 (C-12)O (230 GHz) and (C-13)O (220 GHz) spectra of Mars obtained during the particularly favorable opposition of Mars in 1988 are analyzed. A CO mixing ratio is derived for November 1988 which agrees with a determination from 1967 observations. It is demonstrated that if the mixing ratio of CO was not drastically different in early 1980 and early 1982, the low- to midlatitude average thermal structure of the Mars atmosphere at these times was consistent with clear-air radiative-convective equilibrium conditions. Mars atmospheric temperature profiles derived from (C-12)O spectra are also presented.
Clancy, R. Todd↗
Millimeter, microwave, hard X-ray, and soft X-ray observations of energetic electron populations in solar flares
We present comparisons of multiwavelength data for a number of solar flares observed during the major campaign of 1991 June. The different wavelengths are diagnostics of energetic electrons in different energy ranges: soft X-rays are produced by electrons with energies typically below 10 keV, hard X-rays by electrons with energies in the range 10-200 keV, microwaves by electrons in the range 100 keV-1 MeV, and millimeter-wavelength emission by electrons with energies of 0.5 MeV and above. The flares in the 1991 June active period were remarkable in two ways: all have very high turnover frequencies in their microwave spectra, and very soft hard X-ray spectra. The sensitivity of the microwave and millimeter data permit us to study the more energetic (greater than 0.3 MeV) electrons even in small flares, where their high-energy bremsstrahlung is too weak for present detectors. The millimeter data show delays in the onset of emission with respect to the emissions associated with lower energy electrons and differences in time profiles, energy spectral indices incompatible with those implied by the hard X-ray data, and a range of variability of the peak flux in the impulsive phase when compared with the peak hard X-ray flux which is two orders of magnitude larger than the corresponding variability in the peak microwave flux. All these results suggest that the hard X-ray-emitting electrons and those at higher energies which produce millimeter emission must be regarded as separate populations. This has implications for the well-known 'number problem' found previously when comparing the numbers of non thermal electrons required to produce the hard X-ray and radio emissions.
Kundu, M. R.↗
Corrections regarding the Lellouch et al. (1989) analysis of Mars atmospheric C-12O and C-13O spectra
Lellouch et al. (1989) obtained atmospheric CO mixing ratios from Martian C-12O and C-13O microwave spectra that were 3-5 times greater than the Kaplan et al. (1969) IR measurememts; they also inferred a factor-of-2 increase in atmospheric CO abundance between September, 1986 and January, 1987. A reanalysis has been conducted of the Lellouch material, and more detailed treatment of the radiative transfer analysis indicates that its observations are consistent with the Kaplan CO volume mixing ratio determination. It is also ascertained that the Lellouch atmospheric temperature profiles are in error, with no evidence being found for the extreme temperature inversions inferred for the lowest 5 km of the Martian atmosphere.
Clancy, R. Todd↗
A selective review of ground based passive microwave radiometric probing of the atmosphere
The absorption of the various atmospheric constituents with significant microwave spectra is reviewed. Based on the available data, an estimate is made of the uncertainty in the microwave absorption coefficients of the major constituents, water vapor and oxygen. Then there is an examination of the integral equations which describe the three basic types of observations: measurement of the spectrum of absorption of the sun's radiation by an atmospheric constituent, measurement of the emission spectrum of a constituent, and measurement at one frequency of the zenith angle dependence of the absorption or emission of the atmosphere.
Welch, W. J.↗
Time variations in the OH microwave and infrared emission from late-type stars
The results of a study initiated in the fall of 1969 are reported. The study was concerned with the monthly measurement of the microwave spectra at 1612 MHz and the broadband infrared fluxes at six wavelengths for 10 OH/IR sources. The observations represent the first conclusive evidence for well-defined, periodic variations in the flux from any type of OH microwave emitter. Following the discovery of OH/IR stars that emit mainly at 1665 and/or 1667 MHz the program was expanded to include four of these sources.
Harvey, P. M.↗
Thermal radio emission from Jupiter and Saturn
Microwave brightness temperature calculations have been carried out for a number of model atmospheres for Jupiter and Saturn. The models considered are characterized by helium to hydrogen number mixing ratios which range from 0 to 0.2. Gaseous ammonia is assumed to be a trace constituent in all the models. The ammonia abundance below the (NH3) cloud level is a free parameter which is determined by comparing the observed thermal spectrum of Jupiter and the total spectrum of Saturn with the model calculations. The theoretical microwave spectra corresponding to those models in which the ammonia abundance is that expected from an atmosphere containing a solar abundance of elements are found to be in generally good agreement with the observations. This result is shown to be nearly independent of the helium to hydrogen ratio for the models considered. There is no evidence at this time that a non-thermal component contributes to Saturn's microwave spectrum.
Gulkis, S.↗
Electron trapping in evolving coronal structures during a large gradual hard X-ray/radio burst
Gradual hard X-ray/radio bursts are characterized by their long duration, smooth time profile, time delays between peaks at different hard X-ray energies and microwaves, and radiation from extended sources in the low and middle corona. Their characteristic properties have been ascribed to the dynamic evolution of the accelerated electrons in coronal magnetic traps or to the separate acceleration of high-energy electrons in a 'second step' process. The information available so far was drawn from quality considerations of time profiles or even only from the common occurrence of emissions in different spectral ranges. This paper presents model computations of the temporal evolution of hard X-ray and microwave spectra, together with a qualitative discussion of radio lightcurves over a wide spectral range, and metric imaging observations. The basis hypothesis investigated is that the peculiar 'gradual' features can be related to the dynamical evolution of electrons injected over an extended time interval in a coronal trap, with electrons up to relativistic energies being injected simultaneously. The analyzed event (26 April. 1981) is particularly challenging to this hypothesis because of the long time delays between peaks at different X-ray energies and microwave frequencies. The observations are shown to be consistent with the hypothesis, provided that the electrons lose their energy by Coulomb collisions and possibly betatron deceleration. The access of the electrons to different coronal structures varies in the course of the event. The evolution and likely destabilization of part of the coronal plasma-magnetic field configuration is of crucial influence in determining the access to these structures and possibly the dynamical evolution of the trapped electrons through betatron deceleration in the late phase of the event.
Bruggmann, G.↗
Microwave Observations of Precipitation and the Atmosphere
This research effort had three elements devoted to improving satellite-derived passive microwave retrievals of precipitation rate: morphological rain-rate retrievals, warm rain retrievals, and extension of a study of geostationary satellite options. The morphological precipitation-rate retrieval method uses for the first time the morphological character of the observed storm microwave spectra. The basic concept involves: 1) retrieval of point rainfall rates using current algorithms, 2) using spatial feature vectors of the observations over segmented multi-pixel storms to estimate the integrated rainfall rate for that storm (cu m/s), and 3) normalization of the point rain-rate retrievals to ensure consistency with the storm-wide retrieval. This work is ongoing, but two key steps have been completed: development of a segmentation algorithm for defining spatial regions corresponding to single storms for purposes of estimation, and reduction of some of the data from NAST-M that will be used to support this research going forward. The warm rain retrieval method involved extension of Aquai/AIRS/AMSU/HSB algorithmic work on cloud water retrievals. The central concept involves the fact that passive microwave cloud water retrievals over approx. 0.4 mm are very likely associated with precipitation. Since glaciated precipitation is generally detected quite successfully using scattering signatures evident in the surface-blind 54- and 183-GHz bands, this new method complements the first by permitting precipitation retrievals of non-glaciated events. The method is most successful over ocean, but has detected non-glaciated convective cells over land, perhaps in their early formative stages. This work will require additional exploration and validation prior to publication. Passive microwave instrument configurations for use in geostationary orbit were studied. They employ parabolic reflectors between 2 and 4 meters in diameter, and frequencies up to approx.430 GHz; this corresponds to nadir spot diameters as small as 10 km.
Staelin, David H.↗
Bond Length Alternation and Internal Dynamics in Model Aromatic Substituents of Lignin
In this report broadband microwave spectra were recorded over the 2-18 GHz frequency range for a series of four model aromatic components of lignin; namely, guaiacol (ortho-methoxy phenol, G), syringol (2,6-dimethoxy phenol, S), 4-methyl guaiacol (MG), and 4-vinyl guaiacol (VG), under jet-cooled conditions in the gas phase. Using a combination of 13 C isotopic data and electronic structure calculations, distortions of the phenyl ring by the substituents on the ring are identified. In all four molecules, the r C(1)-C(6) bond between the two substituted C-atoms lengthens, leading to clear bond alternation that reflects an increase in the phenyl ring resonance structure with double bonds at r C(1)-C(2) , r C(3)-C(4) and r C(5)-C(6) . Syringol, with its symmetric methoxy substituents, possesses a microwave spectrum with tunneling doublets in the a-type transitions associated with H-atom tunneling. These splittings were fit to determine a barrier to hindered rotation of the OH group of 1975 cm -1 , a value nearly 50% greater than that in phenol, due to the presence of the intramolecular OH…OCH 3 H-bonds at the two equivalent planar geometries. In 4-methyl guaiacol, methyl rotor splittings are observed and used to confirm and refine an earlier measurement of the three-fold barrier V 3 = 67 cm -1 . Finally, 4-vinyl guaiacol shows transitions due to two conformers differing in the relative orientations of the vinyl and OH groups.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Capturing CO 2 in Quadrupolar Binding Pockets: Broadband Microwave Spectroscopy of Pyrimidine-(CO 2 ) n , n = 1,2
Pyrimidine has two in-plane CH(δ+)/N̈(δ–)/CH(δ+) binding sites that are complementary to the (δ–/2δ+/δ–) quadrupole moment of CO 2 . For this study, we recorded broadband microwave spectra over the 7.5–17.5 GHz range for pyrimidine-(CO 2 ) n with n = 1 and 2 formed in a supersonic expansion. Based on fits of the rotational transitions, including nuclear hyperfine splitting due to the two 14 N nuclei, we have assigned 313 hyperfine components across 105 rotational transitions for the n = 1 complex and 208 hyperfine components across 105 rotational transitions for the n = 2 complex. The pyrimidine-CO 2 complex is planar, with CO 2 occupying one of the quadrupolar binding sites, forming a structure in which the CO 2 is stabilized in the plane by interactions with the C–H hydrogens adjacent to the nitrogen atom. This structure is closely analogous to that of the pyridine-CO 2 complex studied previously by (Doran, J. L. J. Mol. Struct. 2012, 1019, 191–195). The fit to the n = 2 cluster gives rotational constants consistent with a planar cluster of C 2v symmetry in which the second CO 2 molecule binds in the second quadrupolar binding pocket on the opposite side of the ring. The calculated total binding energy in pyrimidine-CO 2 is –13.7 kJ mol –1 , including corrections for basis set superposition error and zero-point energy, at the CCSD(T)/ 6-311++G(3df,2p) level, while that in pyrimidine-(CO 2 ) 2 is almost exactly double that size, indicating little interaction between the two CO 2 molecules in the two binding sites. The enthalpy, entropy, and free energy of binding are also calculated at 300 K within the harmonic oscillator/rigid-rotor model. This model is shown to lack quantitative accuracy when it is applied to the formation of weakly bound complexes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗