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IR and Raman spectra of solid and matrix isolated methylamine and deuterium derivatives, locating amine twisting vibration in solid phase IR spectra
High-valence actinide oxides are critical to understanding the behavior of 5f-electrons, yet their structural and electronic properties remain poorly understood due to challenges in synthesis and handling. We report the first Raman spectroscopic study of single-crystalline Np 2 O 5 and the first scanning tunneling spectroscopy (STS) measurement on any neptunium-containing material. Hydrothermally synthesized crystals were structurally verified by X-ray diffraction. Raman spectra revealed sharply resolved vibrational features, including previously unreported low-frequency modes. STS measurements revealed a band gap of 1.5 eV. Density functional theory (DFT) enables vibrational mode assignments, reveals neptunium-dominated low-frequency phonons, oxygen-dominated high-frequency modes, and predicts an indirect band gap of 1.68 eV. This predicted value is in excellent agreement with the experimentally measured STS gap. This combined Raman, DFT, and STS approach provides a robust framework for correlating lattice dynamics and electronic structure in actinide materials, providing benchmark data for Np 2 O 5 , and opening new avenues for probing structure–property relationships in complex f-electron materials.
The main objective of the proposal was to model the collision induced, second overtone band of gaseous hydrogen at low temperatures. The aim of this work is to assist planetary scientists in their investigation of planetary atmospheres, mainly those of Uranus and Neptune. The recently completed extended database of collision induced dipole moments of hydrogen pairs allowed us, for the first time, to obtain dipole moment matrix elements responsible for the roto-vibrational collision induced absorption spectra of H2-H2 in the second overtone band. Despite our numerous attempts to publish those data, the enormous volume of the database did not allow us to do this. Instead, we deposited the data on a www site. The final part of this work has been partially supported by NASA, Division for Planetary Atmospheres. In order to use our new data for modelling purpose, we first needed to test how well we can reproduce the existing experimental data from theory, when using our new input data. Two papers resulted from this work. The obtained agreement between theoretical results and the measurements appeared to be within 10-30%. The obviously poorer agreement than observed for the first H2 overtone, the fundamental, and the rototranslational bands can be attributed to the fact that dipole moments responsible for the second overtone are much weaker, therefore susceptible to larger numerical uncertainties. At the same time, the intensity of the second overtone band is much weaker and therefore it is much harder to be measured accurately in the laboratory. We need to point out that until now, no dependable model of the 2nd overtone band was available for modelling of the planetary atmospheres. The only one, often referred to in previous works on Uranian and Neptune's atmospheres, uses only one lineshape, with one (or two) parameter(s) deduced at the effective temperature of Uranus (by fitting the planetary observation). After that, the parameter(s) was(were) made temperature dependent according to some very simple relation. Summarizing, no reliable temperature-dependent model has been available yet. Our approach was a bit different from similar attempts done earlier, on account of the poorer agreement of theory with experiment. We needed to resort to some semi-empirical procedure. While we were in a favourable position to be able to rely on the physical input data, these, apparently, did not supply the most dependable predictions (simply because the results did not agree well enough with experimental data). On the other hand, the relative deviations between the theory and experiment were comparable at 77 and at 298 K. That fact indicated that theory is capable of predicting the temperature dependence of the absorption spectra well. We have thus chosen the "middle way". We have fitted the existing measurements with many 3- parameter lineshapes, in order to achieve the closest fit.
A simple curve-of-growth technique is described for extracting the C-12/C-13 ratio for M stars from high-resolution spectra of CO infrared vibration-rotation lines. The technique is applied to the CO lines at 1.6 and 2.3 microns in spectra of two M supergiants (Alpha Ori and Alpha Sco), two M giants (Alpha Her and Beta Peg), and a Mira-type variable (Chi Cyg). As a check on the CO analysis, the C-12/C-13 ratio is derived from the red CN system at 8000 A for Alpha Sco, Alpha Ori, and Beta Peg. The CO analysis is also applied to the K giant Alpha Boo as a check. The CN and CO results are found to be in general agreement, and the C-12/C-13 ratio in all the examined stars is shown to be considerably lower than the solar-system value. It is suggested that these stars were formed from clouds with a C-12/C-13 ratio of 40 to 89 and that their atmospheres now exhibit an enhancement of C-13 abundance due to internal production and mixing to the surface.
Microwave spectra of 1-methylpentaborane /9/ noting vibration-rotation interactions, molecular structure and dipole moment
This Tutorial provides a step-by-step guide on how to apply supervised machine-learning techniques to analyze diffraction and spectroscopy data. This Tutorial details four models—a reconstruction-focused model, a regression-focused model, a hybrid reconstruction/regression model, and a multimodal model—that use x-ray diffraction profiles and vibrational density of states spectra to predict various microstructural descriptors. In this Tutorial, we cover data pre-processing steps, constructions of the models via dimensionality reduction and regression, training, and analysis of these models. Comparisons of the model’s performance are provided, highlighting the strength and weakness of the various approaches utilized.
Kramers-Kronig analysis is applied to measured values of spectral reflectance at near-normal incidence to determine the real and the imaginary parts of the complex index of refraction for methane, ethane, propane, n-butane, n-hexane, n-heptane, and n-decane in the liquid state. The results indicate that the strengths of the characteristic bands as measured by the integral of the imaginary part are roughly constant for all the liquid alkanes except for methane. The intensity of the CH valence vibration bands in the spectra of the alkanes except methane is directly proportional to the number of CH groups per unit volume. The relations for the intensity of the bands due to CH2 and CH3 deformations are examined. Characteristic band intensities of the type established for NH4(+) and SO4(2-) groups in solutions and crystals cannot be extended to the more closely coupled CH2 and CH3 groups in alkane molecules.
The rotational spectra of IO in vibrational states up to v = 13 in the X(sub 1) (sup 2)pi(sub 3/2) state and up to v = 9 in the X2 (sup 2)pi(sub 1/2) state have been observed in an O2 discharge over molecular I2. In addition, I(18)O has been observed for both the X(sub 1) and X(sub 2) states up to v = 5. All data have been analyzed simultaneously with fixed isotopic ratios among the constants. This extends the data set for the X(sub 1) state described last year at this meeting and provides the first high resolution data for the X(sub 2) state and for I(18)O. An extensive set of parameters has been derived. These will be interpreted in terms of the electronic structure and the interatomic potential.
The potential effects of high frequency vibrations on the final Thematic Mapper (TM) image are evaluated for 26 scenes. The angular displacements of the TM detectors from their nominal pointing directions as measured by the TM Angular Displacement Sensor (ADS) and the spacecraft Dry Rotor Inertial Reference Unit (DRIRU) give data on the along scan and cross scan high frequency vibrations present in each scan of a scene. These measurements are to find the maximum overlap and underlap between successive scans, and to analyze the spectrum of the high frequency vibrations acting on the detectors. The Fourier spectrum of the along scan and cross scan vibrations for each scene also evaluated. The spectra of the scenes examined indicate that the high frequency vibrations arise primarily from the motion of the TM and MSS mirrors, and that their amplitudes are well within expected ranges.
Two-dimensional infrared spectroscopy offers unique capabilities for probing vibrational coupling in complex metal–ligand systems. In this paper, we combine two-dimensional infrared spectroscopy with vibrational perturbation theory to investigate vibrational coupling in a diiron trinitrosyl complex across three stable redox states. Although these systems are challenging for electronic structure methods, we demonstrate that key features of experimental 2D IR spectra can be accurately reproduced using reduced-dimensional anharmonic calculations with a small harmonic frequency scaling. Analysis reveals that N–O stretching modes maintain high locality across all redox states, with coupling patterns that directly reflect variations in Fe–N bond strength. Using curvilinear coordinate analysis, we demonstrate these differences result from systematic changes in cubic anharmonic force constants rather than mode delocalization. Our results establish N–O stretches as sensitive probes of metal–ligand bonding strength, expanding the toolkit for studying biologically relevant nitrosyl complexes.
A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.
In recent years there has been interest in incorporating substituted 1,4-naphthoquinones (NQs) into the A 1 binding site in photosystem I (PSI) photosynthetic protein complexes. This interest in part stems from the considerably altered bioenergetics of electron transfer that occur in PSI with such substitutions. Time resolved FTIR studies of PSI complexes with disubstituted NQs incorporated have and currently are being undertaken, and with this in mind it is worth considering FTIR absorption spectra of these disubstituted NQs in solution. Here we present FTIR absorbance spectra for 2-bromo-3-methyl-1,4-naphthoquinone (BrMeNQ), 2-chloromethyl-3-methyl-1,4-naphthoquinone (CMMeNQ) and 2-ethylthio-3-methyl-1,4-naphthoquinone (ETMeNQ) in tetrahydrofuran (THF). The FTIR spectra of these di-substituted naphthoquinones (NQs) were compared to FTIR spectra of 2-methyl-3-phytyl-1,4-naphthoquinone [phylloquinone (PhQ)], 2,3-dimethyl-1,4-naphthoquinone (DMNQ), and 2-methyl-1,4-naphthoquinone (2MNQ). To aid in the assignment of bands in the experimental spectra, density functional theory (DFT) based vibrational frequency calculations for all the substituted NQs in solution were undertaken. The calculated and experimental spectra agree well. By calculating normal mode potential energy distributions, unambiguous quantitative band assignments were made. The calculated and experimental spectra together make predictions about what may be observable in time resolved FTIR difference spectra obtained using PSI with the different NQs incorporated. As a result, time resolved FTIR difference spectra are presented that support these predictions.
Urban Air Mobility vehicles are an emerging class of vertical lift vehicles using electric motors to drive multiple rotors for lift. The outrunner electric motors that are commonly used, may be capable of generating noise that could contribute to the vehicle’s overall noise profile and could generate cabin noise. Understanding and predicting the noise requires more knowledge of the rotor vibrations and eventually a model to predict the frequencies of those vibrations. This work presents a measurement of the rotor vibrations of two different small-scale motors. Two techniques to measure the surface vibration were used. The displacement spectra are compared with acoustic measurements. A finite element analysis model is used to predict the rotor resonance frequencies. The predicted frequencies are in fair agreement with the experimentally observed vibration frequencies, but requires further work to understand discrepancies.
The commonly used Franck-Condon (FC) approximation is inadequate for explaining the electronic spectra of compounds that possess vibrations with substantial Herzberg-Teller (HT) couplings. Metal-based tetrapyrrole derivatives, which are ubiquitous natural pigments, often exhibit prominent HT activity. In this paper, we compare the condensed phase spectra of zinc-tetraphenylporphyrin (ZnTPP) and zinc-phthalocyanine (ZnPc), which exhibit vastly different spectral features in spite of sharing a common tetrapyrrole backbone. The absorption and emission spectra of ZnTPP are characterized by a lack of mirror symmetry and nontrivial temperature dependence. In contrast, mirror symmetry is restored, and the nontrivial temperature-dependent features disappear in ZnPc. We attribute these differences to FC-HT interference, which is less pronounced in ZnPc because of a larger FC component in the dipole moment that leads to FC-dominated transitions. A single minimalistic FC-HT vibronic model reproduces all the experimental spectral features of these molecules. These observations suggest that FC-HT interference is highly susceptible to chemical modification.
Two-dimensional hybrid organic–inorganic perovskites (HOIPs) have emerged as promising materials for light-emitting diode applications. In this study, by using time-of-flight neutron spectroscopy we identified and quantitatively separated the lattice vibrational and molecular rotational dynamics of two perovskites, butylammonium lead iodide (BA)2PbI4 and phenethyl-ammonium lead iodide (PEA) 2 PbI 4 . By examining the corresponding temperature dependence, we found that the lattice vibrations, as evidenced by neutron spectra, are consistent with the lattice dynamics obtained from Raman scattering. We revealed that the rotational dynamics of organic molecules in these materials tend to suppress their photoluminescence quantum yield (PLQY) while the vibrational dynamics did not show predominant correlations with the same. Additionally, we observed photoluminescence emission peak splitting for both systems, which becomes prominent above certain critical temperatures where the suppression of PLQY begins. This study suggests that the rotational motions of polarized molecules may lead to a reduction in exciton binding energy or the breaking of degeneracy in exciton binding energy levels, enhancing non-radiative recombination rates, and consequently reducing photoluminescence yield. These findings offer a deeper understanding of fundamental interactions in 2D HOIPs and could guide the design of more efficient light-emitting materials for advanced technological applications.
In our proposal we laid out work in three areas of relevance to atmospheric science: millimeter and submillimeter spectroscopy, variable temperature pressure broadening, and band and intensity measurements in the FIR. Below we will briefly discuss our progress during the second year of this project. In our millimeter and submillimeter (mm/submm) spectroscopic work, one of our goals has been to work towards the unification of the rotational (primarily obtained by mm/submm techniques) and rotational-vibrational (primarily obtained by infrared techniques) data sets in the context of theoretically well founded models which take advantage of the strengths of the data from each experimental technique. From the point of view of the development of the optimal data base for atmospheric observations, this is clearly a desirable goal. During the first year of this project we did an analysis of a weighted, mixed infrared and mm/submm data set of the n = 0, 1, and 2 torsional states of the ground vibrational state of HOOH. The purpose of this work is to provide a unified understanding of the spectrum, which is applicable in both the rotational and rotational - vibrational regimes. We have succeed in doing this in the context of a single weighted fit which accounts for both data sets to their respective experimental uncertainty (-0.1 and 10 MHz, respectively). Additionally, we have now done a similar analysis on the n = 0 torsional state of v(sub 3) and begun a similar analysis on v(sub 6). For several years we have been working on the mm/submm rotational spectra of the many excited vibrational states of HNO3, again with particular emphasis on the relationships between the mm/submm and infrared spectra. During the first year of this project we were able to use mm/submm spectroscopy to fully resolve the torsional splittings in 2 v(sub 9) and v(sub 5), establish a theoretically well founded quantitative relation between them, and show that both have their physical origin in the torsional motion of the v(sub 9) mode.This result has now been incorporated in a recent reanalysis of the infrared spectrum and has resulted in improved fits - eliminating what was in retrospect a systematic error associated with this previously unknown effect.
Infrared solar spectra in the 850 to 1350/cm region, at 0.02/cm resolution, were obtained during a balloon flight made on 27 October 1978 from Alamogordo, New Mexico. Analysis of the 1275-1290/cm region indicates that the atmospheric absorption lines of CH4, N2O, H2O, HNO3 and CO2 near 1283/cm are super-imposed on a broader absorption feature which we interpret as due to the V3 band of CF4. Fine structure of CF4 is also identified. Preliminary estimates from the sunset spectra show approximately 75 pptv CF4 near 25 km.