Molecular spectroscopic research Final technical report
Quadrupole rotation-vibration spectrum of hydrogen and predissociation rates of B state of iodine
James, T. C.↗
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Dust emission in the Sagittarius B2 molecular cloud core
A model is presented for the dust emission from the Sagittarius B2 molecular cloud core which reproduces the observed spectrum between 30 and 1300 micron, as well as the distribution of the emission at 1300 micron. The model is based on the assumption that Sgr B2(N) continuum source is located behind the dust cloud associated with Sgr B2(M) continuum source. The fact that Sgr B2(N) is stronger at 1300 micron can be attributed to a local column density maximum at the position of this source. Absence of a 53 micron emission peak at the position of Sgr B2(N) suggests that the luminosity of the north source is lower than that of the middle source.
Lis, Dariusz C.↗
Atomistic simulations and machine learning of solute grain boundary segregation in Mg alloys at finite temperatures
Understanding solute segregation thermodynamics is the first step in investigating grain boundary (GB) properties, such as strong yttrium (Y) effects on grain growth and texture evolution in micro-scale polycrystalline magnesium (Mg) alloys. To estimate the average GB segregation behavior in low-solute-concentration Mg alloys (e.g., 2 at.% Y), a state-of-the-art spectral approach is applied based on a per-site segregation energy spectrum for Y solute atoms at zero K obtained from molecular statistics (MS) simulations of ~10 4 GB sites in Mg symmetric tilt GBs (STGBs). Although selected MS simulation results are consistent with verification by density functional theory (DFT) calculations, estimates of average segregation tendency based on the zero-K energy spectrum deviate from experimental observations. To resolve this problem, thermodynamic integration (TI) methods based on molecular dynamics (MD) simulations are used to determine the per-site segregation free energies of Y at representative GB sites, which show contributions beyond harmonic approximations can be important for certain GB sites at high temperatures. A surrogate model of per-site segregation free energy is constructed from a small set of TI data points using stacking cross-validation regressors and physics-informed descriptors. This model is applied to predict the Y segregation free energy spectra for thousands of GB sites in Mg STGBs with uncertainty quantification. Finally, the average segregation tendency predicted by the spectral approach based on the free energy spectra agrees well (within the uncertainty range) with experimental observations for micro-scale polycrystalline Mg alloys at typical thermomechanical processing temperatures (500 ~ 800 K), where thermodynamic equilibrium states are likely to be achieved due to fast diffusion.
Atomistic simulations↗
OGO-4 observations of the ultraviolet auroral spectrum
Auroral ultraviolet spectra in the range from 1200 to 3200 A have been obtained by the spectrometer on board the OGO-4 satellite. Emissions of N2, H, O, and N are readily identified. Atomic and molecular intensities are deduced from the comparison with a synthetic spectrum and compare reasonably well with some previous measurements and calculations. A feature at 2150 A is assigned to the (1-0) NO gamma band. Taking into consideration the various excitation mechanisms of NO(A2 Sigma), it is proposed that energy transfer from N2 metastable molecules to oxygen accounts for the excitation of the NO gamma bands. In particular, it is suggested that the resonant reaction between O2 and highly metastable N2 molecules may be a major source of NO(A2 Sigma).
Gerard, J.-C.↗
Molecular astronomy at submillimeter wavelengths
It is pointed out that the region of the spectrum from 300 to 3000 GHz (100 to 1000 microns), which is referred to as the submillimeter, is one of the least explored areas in the electromagnetic spectrum. The reasons for this situation are related to a lack of adequate instrumentation for detecting the radiation and an almost complete absorption of the radiation by the earth's atmosphere. The vast majority of the rotational transitions of molecules occur in the millimeter and submillimeter wavelength region of the spectrum. The strength of the lines increases at higher frequencies until a condition is reached in which the energy levels are no longer populated. The study of molecular clouds at submillimeter wavelengths promises to provide new important results. Attention is given to the design of suitable submillimeter receivers, problems of atmospheric transmission, and galactic molecular lines.
Buhl, D.↗
Probing ferroelectricity by x-ray absorption spectroscopy in molecular crystals
We carry out x-ray absorption spectroscopy experiment at the oxygen $K$ edge in croconic acid (C 5 H 2 O 5 ) crystal as a prototype of ferroelectric organic molecular solid, whose electric polarization is generated by proton transfer. The experimental spectrum is well reproduced by the electron-hole excitation theory simulations from configuration generated by ab initio molecular dynamics simulation. When inversion symmetry is broken in the ferroelectric state, the hydrogen bonding environment on the two bonded molecules become inequivalent. Such a difference is sensitively probed by the bound excitation in the pre-edge, which is strongly localized on the excited molecules. Our analysis shows that a satellite peak in the pre-edge will emerge at higher excitation energy, which serves as a clear signature of ferroelectricity in the material.
36 MATERIALS SCIENCE↗
Closed-Shell Polycyclic Aromatic Hydrocarbon Cations: A New Category of Interstellar Polycyclic Aromatic Hydrocarbons
Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.
Hudgins, Douglas M.↗
Optical functions for molecular hydrogen Final report
Franck-Condon factors calculated for vibrational energy level transitions in molecular hydrogen band systems
VIBRATIONAL SPECTRUM↗
Molecular attenuation and phase dispersion between 40 and 140-GHz for path models from different altitudes
Radio wave propagation in the 40 to 140 GHz band through the first hundred kilometers of the atmosphere is strongly influenced by the microwave spectrum of oxygen (O2-MS). A unified treatment of molecular attenuation and phase dispersion is formulated. Results of molecular physics are translated into frequency, temperature, pressure, and magnetic field dependencies of a complex refractive index. The intensity distribution of the O2-MS undergoes several changes with increasing altitude. The influence of water vapor is discussed. Examples of computer plots are given as a function of altitude for homogeneous, zenith, and tangential path geometries. Molecular resonances of minor atmospheric gases are discussed briefly.
Liebe, H. J.↗
Molecular fluorescence as a monitor of minor stratospheric constituents
The potential of molecular fluorescence was assessed as a stratospheric monitor of the concentrations of various minor species. Seventeen molecules were considered and all spectral regions from the vacuum ultraviolet through to the infrared are included. The exercise has produced few surprises; however, further confirmation has emerged as to the feasibility of this sensitive technique for monitoring stratospheric OH, NO2, and SO2, sufficient to warrant its development as analytical flight hardware for these species. All the other molecules have been eliminated with the exception of C10 which appears to have promise but requires additional information before its detection limit can be calculated; its fluorescence spectrum is as yet uninvestigated. A handbook for molecular fluorescence is presented, and a compilation of all reported studies for simple molecules using line source excitation is included.
Schofield, K.↗
Spectroscopic detection of molecular hydrogen frozen in interstellar ices
A weak infrared absorption feature near 4141 wavenumbers (2.415 micrometers) in the spectrum of WL5, an infrared source in the rho Ophiuchus cloud complex, has been detected. It is attributed to molecular hydrogen created by irradiation and frozen in situ into water-rich ices. A second, broader absorption at 4125 wavenumbers centimeters (2.424 micrometers) is probably due to methanol in the ices. The column densities of frozen molecular hydrogen and methanol are inferred to be about 2.5 x 10(exp 18) and 3.0 x 10(exp 19), respectively. There is about three times more frozen molecular hydrogen than frozen carbon monoxide along this line of sight.
Sandford, Scott A.↗
Absolute transition probabilities in the ultraviolet spectrum of co.
UV spectrum of CO molecule, determining absolute transition probabilities from radiation lifetime and relative radiation branching ratio
MOLECULAR SPECTROSCOPY↗
Absolute oscillator strengths of the strongest bands within the dipole-allowed absorption spectrum of nitrogen.
Absolute absorption values of four strongest bands in molecular N dipole, determining oscillator strengths
Dressler, K.↗
Research Investigation Directed Toward Extending the Useful Range of the Electromagnetic Spectrum
The report discusses completed and proposed research in atomic and molecular physics conducted at the Columbia Radiation Laboratory from July 1972 to June 1973. Central topics described include the atomic spectra and electronic structure of alkali metals and helium, molecular microwave spectroscopy, the resonance physics of photon echoes in some solid state systems (including Raman echoes, superradiance, and two photon absorption), and liquid helium superfluidity.
Hartmann, S. R.↗
New narrow infrared absorption features in the spectrum of Io between 3600 and 3100 cm (2.8-3.2 micrometers)
We report the discovery of a series of infrared absorption bands between 3600 and 3100/cm (2.8-3.2 micrometers) in the spectrum of Io. Individual narrow bands are detected at 3553, 3514.5, 3438, 3423, 3411.5, and 3401/cm (2.815, 2.845, 2.909, 2.921, 2.931, and 2.940 micrometers, respectively). The positions and relative strengths of these bands, and the difference of their absolute strengths between the leading and trailing faces of Io, indicate that they are due to SO2. The band at 3438/cm (2.909 micrometers) could potentially have a contribution from an additional molecular species. The existence of these bands in the spectrum of Io indicates that a substantial fraction of the SO2 on Io must reside in transparent ices having relatively large crystal sizes. The decrease in the continuum observed at the high frequency ends of the spectra is probably due to the low frequency side of the recently detected, strong 3590/cm (2.79 micrometer) feature. This band is likely due to the combination of a moderately strong SO2 band and an additional absorption from another molecular species, perhaps H2O isolated in SO2 at low concentrations. A broad (FWHM approximately = 40-60/cm), weak band is seen near 3160/cm (3.16 micrometers) and is consistent with the presence of small quantities of H2O isolated in SO2-rich ices. There is no evidence in the spectra for the presence of H2O vapor on Io. Thus, the spectra presented here neither provide unequivocal evidence for the presence of H2O on Io nor preclude it at the low concentrations suggested by past studies.
Sandford, Scott A.↗
The Far-Infrared Polarization Spectrum of Ρ Ophiuchi A from HAWC+/SOFIA Observations
We report on polarimetric maps made with HAWC+/SOFIA toward ρ Oph A, the densest portion of the ρ Ophiuchi molecular complex. We employed HAWC+ bands C (89 μm) and D (154 μm). The slope of the polarization spectrum was investigated by defining the quantity R(sub DC) = p(sub D)/p(sub C), where p(sub C) and p(sub D) represent polarization degrees in bands C and D, respectively. We find a clear correlation between R(sub DC) and the molecular hydrogen column density across the cloud. A positive slope (R(sub DC) > 1) dominates the lower-density and well- illuminated portions of the cloud, which are heated by the high-mass star Oph S1, whereas a transition to a negative slope (R(sub DC) < 1) is observed toward the denser and less evenly illuminated cloud core. We interpret the trends as due to a combination of (1) warm grains at the cloud outskirts, which are efficiently aligned by the abundant exposure to radiation from Oph S1, as proposed in the radiative torques theory; and (2) cold grains deep in the cloud core, which are poorly aligned owing to shielding from external radiation. To assess this interpretation, we developed a very simple toy model using a spherically symmetric cloud core based on Herschel data and verified that the predicted variation of R(sub DC) is consistent with the observations. This result introduces a new method that can be used to probe the grain alignment efficiency in molecular clouds, based on the analysis of trends in the far-infrared polarization spectrum.
Santos, Fabio P.↗
Electrically tuned hyperfine spectrum in neutral Tb( II )(Cp iPr5 ) 2 single-molecule magnet
Molecular spin qubits with long spin coherence time as well as non-invasive operation methods on such qubits are in high demand. It was shown that both molecular electronic and nuclear spin levels can be used as qubits. In solid state systems with dopants, an electric field was shown to effectively change the spacing between the nuclear spin qubit levels when the electron spin density is high at the nucleus of the dopant. Inspired by such solid-state systems, we propose that divalent lanthanide (Ln) complexes with an unusual electronic configuration of Ln 2+ have a strong interaction between the Ln nuclear spin and the electronic degrees of freedom, which renders electrical tuning of the interaction. Furthermore, as an example, we study electronic structure and hyperfine interaction of the 159 Tb nucleus in a neutral Tb(II)(Cp iPr5 ) 2 single-molecule magnet (SMM), which exhibits unusually long magnetization relaxation time, using the complete active space self-consistent field (CASSCF) method with spin–orbit interaction included within the restricted active space state interaction (RASSI). Our calculations show that the low-energy states arise from 4f 8 (6s,5d z 2 ) 1 , 4f 8 (5d x 2 -y 2 ) 1 , and 4f 8 (5d xy ) 1 configurations. We compute the hyperfine interaction parameters and the electronic–nuclear spectrum within our multiconfigurational approach. We find that the hyperfine interaction is about one order of magnitude greater than that for Tb(III)Pc 2 SMMs. This stems from the strong Fermi contact interaction between the Tb nuclear spin and the electron spin density at the nucleus that originates from the occupation of the (6s,5d) orbitals. We also uncover that the response of the Fermi contact term to electric field results in electrical tuning of the electronic–nuclear level separations. This hyperfine Stark effect may be useful for applications of molecular nuclear spins for quantum computing.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dayglow emissions of the O2 Herzberg bands and the Rayleigh backscattered spectrum of the earth
It is pointed out that numerous fluorescent emissions from the Herzberg bands of molecular oxygen lie in the spectral region 242-300 nm. This coincides with the wavelength range used by orbiting spectrometers that observe the Rayleigh backscattered spectrum of the earth for the purpose of monitoring the vertical distribution of stratospheric ozone. Model calculations suggest that Herzberg band emissions in the dayglow could provide significant contamination of the ozone measurements if the quenching rate of O2(A3Sigma) is sufficiently small. It is noted that this is especially true near 255 nm, where the most intense fluorescent emissions relative to the Rayleigh scattered signal are located and where past satellite measurements have shown a persistent excess radiance above that expected for a pure ozone absorbing and molecular scattering atmosphere. Very small quenching rates, however, are adequate to reduce the dayglow emission to negligible levels. Noting that available laboratory data have not definitely established the quenching on the rate of O2(A3Sigma) as a function of vibration level, it is emphasized that such information is required before the Herzberg band contributions can be evaluated with confidence.
Frederick, J. E.↗