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At least 127 records · Page 7

Accurate frequency and intensity measurements of the infrared spectra of atmospheric molecules

Various problems encountered and solutions found in infrared laboratory measurements on atmospheric molecules are discussed. The advantages and limitations of various measurement techniques and equipment are discussed, with emphasis placed on calibration techniques and measurement accuracy and precision. Frequency calibration aids are presented, including the current and planned tables of absorption frequency standards being developed by the Bureau of Standards for the calibration of high-resolution devices with an accuracy of + or - 3 MHz. It is noted that intensity measurements are highly susceptible to systematic errors and that great care must be taken to obtain accuracies better than + or - 10%. What is even more difficult is knowing the accuracy of a particular measurement. Recent work done on providing accurate intensity data are described.

Maki, A. G.↗

What do far-infrared spectra of solitary water in “water-in-solvent” systems reveal about water’s solvation and dynamics?

Classical molecular dynamics simulations of water in ionic and dipolar solvents were used to interpret the far-infrared (FIR) rotation/libration spectra of “solitary water” in terms of water’s rotational dynamics and interactions with solvents. Seven solvents represented by nonpolarizable all-atom force fields and a series of idealized variable-charge solvents were used to span the range of solvent polarities (hydrogen bonding) studied experimentally. Simulated spectra capture the solvent dependence observed, as well as the relationship between the frequencies of water libration (νL) and OH stretching bands (νOH). In more strongly interacting solvents, simulated νL are ∼20% higher than those of experiment. In all solvents, the simulated spectra are composites of rotational motions about the two axes perpendicular to water’s dipole moment, and the different frequencies of these two motions are responsible for the breadth of the libration band and the bimodal shape observed in halide ionic liquids. Simulations overestimate the separation of these two components in most solvents. The character of water rotational motions changes markedly with solvent polarity, from quasi-free rotation in nonpolar and weakly polar solvents to highly constrained libration in strongly hydrogen bonding environments. The changeover to librational motions dominating the spectrum occurs between solvents such as benzene (νL ∼ 250 cm−1) and acetonitrile (νL ∼ 400 cm−1). For solvents in the latter category, the mean frequency of the experimental FIR band provides a direct measure of mean-squared torques and, therefore, force constants associated with interactions constraining water’s librational motion.

Chemistry↗

Utilization of Synthetic Near-Infrared Spectra via Generative Adversarial Network to Improve Wood Stiffness Prediction

Near-infrared (NIR) spectroscopy is widely used as a nondestructive evaluation (NDE) tool for predicting wood properties. When deploying NIR models, one faces challenges in ensuring representative training data, which large datasets can mitigate but often at a significant cost. Machine learning and deep learning NIR models are at an even greater disadvantage because they typically require higher sample sizes for training. In this study, NIR spectra were collected to predict the modulus of elasticity (MOE) of southern pine lumber (training set = 573 samples, testing set = 145 samples). To account for the limited size of the training data, this study employed a generative adversarial network (GAN) to generate synthetic NIR spectra. The training dataset was fed into a GAN to generate 313, 573, and 1000 synthetic spectra. The original and enhanced datasets were used to train artificial neural networks (ANNs), convolutional neural networks (CNNs), and light gradient boosting machines (LGBMs) for MOE prediction. Overall, results showed that data augmentation using GAN improved the coefficient of determination (R 2 ) by up to 7.02% and reduced the error of predictions by up to 4.29%. ANNs and CNNs benefited more from synthetic spectra than LGBMs, which only yielded slight improvement. All models showed optimal performance when 313 synthetic spectra were added to the original training data; further additions did not improve model performance because the quality of the datapoints generated by GAN beyond a certain threshold is poor, and one of the main reasons for this can be the size of the initial training data fed into the GAN. LGBMs showed superior performances than ANNs and CNNs on both the original and enhanced training datasets, which highlights the significance of selecting an appropriate machine learning or deep learning model for NIR spectral-data analysis. The results highlighted the positive impact of GAN on the predictive performance of models utilizing NIR spectroscopy as an NDE technique and monitoring tool for wood mechanical-property evaluation. Further studies should investigate the impact of the initial size of training data, the optimal number of generated synthetic spectra, and machine learning or deep learning models that could benefit more from data augmentation using GANs.

59 BASIC BIOLOGICAL SCIENCES↗

Preliminary results of study of infrared spectra of Venus from the orbital spacecraft Venera-9 and Venera-10

The infrared spectrum of Venus in the spectral range 1.6 to 2.8 was measured by means of the spectrometers aboard 'Venera-9' and 'Venera-10' orbital spacecrafts. Approximately 20 series of measurements were made near the pericenter of the orbit, each of which contains 150 spectra for each path intersecting the planet from the terminator to the limb. Phase angles lie within the limits from 60 to 120 deg.

Gnedykh, V.↗

High-resolution mid-infrared spectra of Co II, Ni I, and Fe II in SN 1987A

Ground-based infrared observations of SN 1987A on day 612 after the explosion have yielded resolved line profiles of Co II, Ni I, Fe II at 10.52, 11.31, and 17.94 micron, respectively. The spectra were taken at a resolving power of about 1000 with an array grating spectrometer on the 4 m telescope of Cerro Tololo Inter-American Observatory. Based on the observed line intensities we have estimated the minimum mass of each ion: M(Co II) = (6.0 +/- 1.8) x 10 exp -5 solar mass; M(Ni I) = (1.1 +/- 0.1) x 10 exp -3 solar mass; and M(Fe II) = (8.0 +/- 1.5) x 10 exp -3 solar mass. From these we infer total masses for cobalt, nickel, and iron in the ejecta. The nickel and iron line profiles are markedly asymmetric. We interpret these as arising from two components, one centered on the stellar rest velocity with an approximately 3250 km/s full width, and the second at about +1200 km/s with an approximately 1100 km/s full width. The asymmetry may represent a large-scale fracturing of the ejecta by Rayleigh-Taylor instabilities.

Jennings, D. E.↗

Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. I. Conformer- and isomer-resolved infrared spectra

Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by infrared (IR) action spectroscopy under jet-cooled conditions with selective detection of hydroxyl (OH) radical products. Two distinct •QOOH isomers with radical sites at a primary carbon of one of the methyl groups (β-Me) or a secondary carbon (β-Et) of the ethyl group are identified by comparison with theoretically calculated IR absorption features for multiple conformers, including C–O, ethyl, and O–O torsions of the two isomers. Here, a master-equation analysis is developed and utilized to explore the conformational cooling process and the resultant conformer population distributions of the two isomers. Most of the IR features observed, including those in the strong fundamental and first overtone OH stretch regions as well as weaker combination bands involving OH stretch with torsion or OOH bend, are in good accord with computed anharmonic frequencies for the most populated conformers of the •QOOH_Et isomer. Relatively weak IR features most evident in the fundamental and first overtone OH stretch regions are ascribed to multiple conformers of the less stable •QOOH_Me isomer, along with a weak feature that is uniquely attributed to a combination band involving asymmetric CH 2 stretch and HCH bend of •QOOH_Me.

Chemical reaction jet spectroscopy↗

Infrared spectra of planetary atmospheres

The development of high spectral resolution and highly sensitive long infrared wavelength instruments is reported. This instrumentation is used to examine molecular lines in planetary atmospheres in enough detail to obtain new information about these atmospheres. Such information includes (1) pressure and temperature relations in planetary atmospheres, and (2) molecular and isotopic composition.

Townes, C. H.↗

Far infrared spectra of H2 mixtures of H2-CH4 and H2-He

Laboratory measurements of the far infrared absorption of H2 and of mixtures of H2 with CH4 and He are presented, and fits to the pure H2 spectra with a semiempirical line shape are described. Such results are needed in analyzing the thermal emission from the atmospheres of the outer planets.

Birnbaum, G.↗

Estimation of Venus wind velocities from high-resolution infrared spectra

Zonal velocity profiles in the Venus atmosphere above the clouds were estimated from measured asymmetries of HCl and HF infrared absorption lines in high-resolution Fourier interferometer spectra of the planet. These asymmetries are caused by both pressure-induced shifts in the positions of the hydrogen-halide lines perturbed by CO2 and Doppler shifts due to atmospheric motions. Particularly in the case of the HCl 2-0 band, the effects of the two types of line shifts can be easily isolated, making it possible to estimate a profile of average Venus equatorial zonal velocity as a function of pressure in the region roughly 60 to 70 km above the surface of the planet. The mean profiles obtained show strong vertical shear in the Venus zonal winds near the cloud-top level, and both the magnitude and direction of winds at all levels in this region appear to vary greatly with longitude relative to the sub-solar point.

Smith, M. A. H.↗

Infrared Spectra and Optical Constants of Elusive Amorphous Methane

New and accurate laboratory results are reported for amorphous methane (CH4) ice near 10 K for the study of the interstellar medium (ISM) and the outer Solar System. Near- and mid-infrared (IR) data, including spectra, band strengths, absorption coefficients, and optical constants, are presented for the first time for this seldom-studied amorphous solid. The apparent IR band strength near 1300 cm(exp −1) (7.69 micrometer) for amorphous CH4 is found to be about 33% higher than the value long used by IR astronomers to convert spectral observations of interstellar CH4 into CH4 abundances. Although CH4 is most likely to be found in an amorphous phase in the ISM, a comparison of results from various laboratory groups shows that the earlier CH4 band strength at 1300 cm(exp −1) (7.69 micrometer) was derived from IR spectra of ices that were either partially or entirely crystalline CH4 Applications of the new amorphous-CH4 results are discussed, and all optical constants are made available in electronic form.

ISM: abundances↗

Water Vapor in Titan's Stratosphere from Cassini CIRS Far-Infrared Spectra

Here we report the measurement of water vapor in Titan's stratosphere using the Cassini Composite Infrared Spectrometer (CIRS). CIRS senses water emissions in the far infrared spectral region near 50 micron, which we have modeled using two independent radiative transfer codes. From the analysis of nadir spectra we have derived a mixing ratio of 0.14 +/- 0.05 ppb at an altitude of 97 km, which corresponds to an integrated (from 0 to 600 km) surface normalized column abundance of 3.7 +/- 1.3 1014 molecules/cm2. In the latitude range 80S to 30N we see no evidence for latitudinal variations in these abundances within the error bars. Using limb observations, we obtained mixing ratios of 0.13 +/- 0.04 ppb at an altitude of 115 km and 0.45 +/- 0.15 ppb at an altitude of 230 km, confirming that the water abundance has a positive vertical gradient as predicted by photochemical models. We have also fitted our data using scaling factors of 0.1-0.6 to these photochemical model profiles, indicating that the models over-predict the water abundance in Titan's lower stratosphere.

composition↗

The significance of far-infrared spectra of the interstellar medium

This paper deals with the analysis of interstellar clouds through infrared and submillimeter observations. The determination of temperature, density, state of ionization and abundance of different chemical constituents is discussed for clouds exhibiting a range of optical depths. There is a preferred choice of spectral features useful for examining different types of gaseous complexes. The prospects for improving the understanding of chemical reaction schemes in interstellar clouds are outlined. Prime advances may be expected in improved data on the abundance of atoms; diatomic hydrides; other small, hydrogen-containing molecules; and their ions.

Harwit, M.↗

Infrared spectra of WC10 planetary nebulae nuclei

The 5.2 to 8.0 micron spectra are presented for two planetary nebulae nuclei Hen1044 (He2-113) and CPD-56 8032. The unidentified infrared (UIR) emission bands at 6.2 microns, 6.9 microns, 7.7 microns are present in the spectra of Hen1044 and in CPD-56 8032, and the 8.6 micron band is present in the long wavelength shoulder of the 7.7 micron band in the spectrum of CPD-56 8032. The 8 to 13 micron spectra of these two stars by Aitken et. al. clearly show the presence of the 8.6 micron band in He2-113 while weakly resolving this feature in the spectra of CPD-56 8032. In their spectra the 11.3 micron band is also clearly detected in both objects. The 6.2 micron and 7.7 micron bands are characteristic of the infrared active C-C stretching modes in polycyclic aromatic hydrocarbons (PAHs); the 3.3 micron, 8.6 micron, and 11.3 micron bands are respectively assigned to the in-plane stretching mode, the in-plane bending mode, and the out-of-plane bending mode of the aromatic CH bond. The weak 6.9 micron emission feature is attributed to the UIR spectrum by Bregman et. al. The IRAS LRS spectra of He2-113 (IRAS 14562-5406) and CPD-56 8032 (IRAS 17047-5650) are presented. Cohen et. al. identify the broad plateau from 11.3 to 13.0 microns in the spectrum of He2-113 with increased hydrogenation of PAHs. This broad plateau is not seen in the LRS spectrum of CPD-56 8032. Also, He2-113 has greater infrared excess emission in the 17-22 micron region than does CPD-56 8032.

Wooden, D. H.↗

Water Vapor in Titan's Stratosphere from Cassini/CIRS Far-infrared Spectra

Since the first detection of water vapor in Titan's stratosphere by disk-average observations from the Infrared Space Observatory (Coustenis et al. 1998) we report here the successful detection of stratospheric water vapor using the Cassini Composite Infrared Spectrometer (CIRS, Flasar et al. 2004). CIRS senses water emissions in the far infrared spectral region near 50 microns, which we have modeled using two independent radiative transfer codes (NEMESIS, Irwin et al 2008 and ART, Coustenis et al. 2007, 2010). From the analysis of nadir spectra we have derived a mixing ratio of (0.14 0.05) ppb at an altitude of 97 kilometers, which corresponds to an integrated (from 0 to 600 kilometers) surface normalized column abundance of (3.7 plus or minus 1.3) x 10(exp 14) molecules per square centimeter. In the latitude range 80 S to 30 N we see no evidence for latitudinal variations in these abundances within the error bars. Using limb observations, we obtained mixing ratios of (0.13 plus or minus 0.04) ppb at an altitude of 115 kilometers and (0.45 plus or minus 0.15) ppb at an altitude of 230 kilometers, confirming that the water abundance has a positive vertical gradient as predicted by photochemical models (e.g. Lara et al. 1996, Wilson and Atreya 2004, Horst et al. 2008); retrieved scaling factors (from approximately 0.1 to approximately 0.6) to the water profile suggested by these models show that water vapor is present in Titan stratosphere with less abundance than predicted.

Cottini, V.↗

Water Vapor on Titan: The Stratospheric Vertical Profile from Cassini/CIRS Infrared Spectra

Water vapor in Titan's middle atmosphere has previously been detected only by disk-average observations from the Infrared Space Observatory (Coustenis et al., 1998). We report here the successful detection of stratospheric water vapor using the Cassini Composite Infrared Spectrometer (CIRS, Flasar et al., 2004) following an earlier null result (de Kok et al., 2007a). CIRS senses water emissions in the far-infrared spectral region near 50 microns, which we have modeled using two independent radiative transfer and inversion codes (NEMESIS, Irwin et al 2008 and ART, Coustenis et al., 2010). From the analysis of nadir spectra we have derived a mixing ratio of (0.14 plus or minus 0.05) ppb at 100 km, corresponding to a column abundance of approximately (3.7 plus or minus 1.3) x 10(exp 14) moles per square centimeter. Using limb observations, we obtained mixing ratios of (0.13 plus or minus 0.04) ppb at 125 km and (0.45 plus or minus 0.15) ppb at 225 km of altitude, confirming that the water abundance has a positive vertical gradient as predicted by photochemical models. In the latitude range (80 deg. S - 30 deg. N) we see no evidence for latitudinal variations in these abundances within the error bars.

Cottini, V.↗

Pyroxene Spectroscopy: Effects of Major Element Composition on Near, Mid and Far-Infrared Spectra

Pyroxene is one of the most common minerals in both evolved and undifferentiated solid bodies of the solar system. Various compositions of pyroxene have been directly studied in meteorites and lunar samples and remotely observed by telescopic and orbital measurements of the moon, Mars, Mercury, and several classes of asteroids. Laboratory studies of pyroxene spectra have shown that absorption features diagnostic of pyroxene in both the near and mid infrared are composition dependent. The challenge for remote analyses has been to reduce the level of ambiguity to allow a quantitative assessment of mineral chemistry. This study focuses on the analysis of a comprehensive set of synthetic Ca-Fe-Mg pyroxenes from the visible through far-IR (0.3-50 m) to address the fundamental constraints of crystal structure on absorption.

Klima, R. L.↗