Dissociation energy and vibrational terms of ground-state
Dissociation energy and vibrational terms of ground state hydrogen
Bernstein, R. B.↗
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A Detailed Level Kinetics Model of NO Vibrational Energy Distributions
Several contemporary problems have pointed to the desirability of a detailed level kinetics approach to modeling the distribution of vibrational energy in NO. Such a model is necessary when vibrational redistribution reactions are insufficient to maintain a Boltzmann distribution over the vibrational energy states. Recent calculations of the rate constant for the first reaction of the Zeldovich mechanism (N2 + O (goes to) NO + N) have suggested that the product NO is formed in high vibrational states. In shock layer flowfields, the product NO molecules may experience an insufficient number of collisions to establish a Boltzmann distribution over vibrational states, thus necessitating a level kinetics model. In other flows, such as expansions of high temperature air, fast, near-resonance vibrational energy exchanges with N2 and O2 may also require a level specific model for NO because of the relative rates of vibrational exchange and redistribution. The proposed report will integrate computational and experimental components to construct such a model for the NO molecule.
Sharma, Surendra P.↗
The internal state distribution of CN radicals produced in the photolysis of HC2CN and CH3CN
The energy partitioning in CN radicals produced by the vacuum ultraviolet photodissociation of HC2CN and CH3CN is studied by means of laser-induced fluorescence of the B-X transition. Experiments are performed in two collision regimes: (1) in the low-collision number regime, the energy partitioning in CN(X) is measured; (2) in the high-collision number regime, the formation of CN(A) is monitored. It is shown that photodissociation of HC2CN in its linear predissociative 1Sigma(+) state produces predominantly ground-state CN in rotationally and vibrationally excited states. The vibrational population ratios and the temperatures computed from a Boltzmann fit of the rotational levels are given in a table. The excitation of CH3CN produces CN radicals almost entirely in the first excited A-state with vibrational excitation.
Cody, R. J.↗
Effect of multiple exposure to vibration on the functional state of the spinal reflex arc
Multiple exposure to vibration and functional state of spinal reflex arc in guinea pigs
VIBRATIONAL STRESS↗
Studies of interstellar vibrationally-excited molecules
Several molecules thus far have been detected in the ISM in vibrationally-excited states, including H2, SiO, HC3N, and CH3CN. In order for vibrational-excitation to occur, these species must be present in unusually hot and dense gas and/or where strong infrared radiation is present. In order to do a more thorough investigation of vibrational excitation in the interstellar medium (ISM), studies were done of several mm-wave transitions originating in excited vibrational modes of HCN, an abundant interstellar molecule. Vibrationally-excited HCN was recently detected toward Orion-KL and IRC+10216, using a 12 meter antenna. The J=3-2 rotational transitions were detected in the molecule's lowest vibrational state, the bending mode, which is split into two separate levels, due to l-type doubling. This bending mode lies 1025K above ground state, with an Einstein A coefficient of 3.6/s. The J=3-2 line mode of HCN, which lies 2050K above ground state, was also observed toward IRC+10216, and subsequently in Orion-KL. Further measurements of vibrationally-excited HCN were done using a 14 meter telescope, which include the observations of the (0,1,0) and (0,2,0) modes towards Orion-KL, via their J=3-2 transitions at 265-267 GHz. The spectrum of the J=3-2 line in Orion taken with the 14 meter telescope, is shown, along with a map, which indicates that emission from vibrationally-excited HCN arises from a region probably smaller than the 14 meter telescope's 20 arcsec beam.
Ziurys, L. M.↗
Planetary Transmission Diagnostics
This report presents a methodology for detecting and diagnosing gear faults in the planetary stage of a helicopter transmission. This diagnostic technique is based on the constrained adaptive lifting algorithm. The lifting scheme, developed by Wim Sweldens of Bell Labs, is a time domain, prediction-error realization of the wavelet transform that allows for greater flexibility in the construction of wavelet bases. Classic lifting analyzes a given signal using wavelets derived from a single fundamental basis function. A number of researchers have proposed techniques for adding adaptivity to the lifting scheme, allowing the transform to choose from a set of fundamental bases the basis that best fits the signal. This characteristic is desirable for gear diagnostics as it allows the technique to tailor itself to a specific transmission by selecting a set of wavelets that best represent vibration signals obtained while the gearbox is operating under healthy-state conditions. However, constraints on certain basis characteristics are necessary to enhance the detection of local wave-form changes caused by certain types of gear damage. The proposed methodology analyzes individual tooth-mesh waveforms from a healthy-state gearbox vibration signal that was generated using the vibration separation (synchronous signal-averaging) algorithm. Each waveform is separated into analysis domains using zeros of its slope and curvature. The bases selected in each analysis domain are chosen to minimize the prediction error, and constrained to have the same-sign local slope and curvature as the original signal. The resulting set of bases is used to analyze future-state vibration signals and the lifting prediction error is inspected. The constraints allow the transform to effectively adapt to global amplitude changes, yielding small prediction errors. However, local wave-form changes associated with certain types of gear damage are poorly adapted, causing a significant change in the prediction error. The constrained adaptive lifting diagnostic algorithm is validated using data collected from the University of Maryland Transmission Test Rig and the results are discussed.
Lewicki, David G.↗
Effect of Solvent on the Local Structure, Dynamics, and Vibrational Density of States in Sn-BEA Zeolite
Lewis acid zeolites are attractive catalysts for epoxidation and biomass valorization, as they are highly active and selective in the liquid phase and can operate at or near ambient conditions. While a rich experimental literature exists on liquid-phase Lewis acid zeolite catalysis, our understanding of the molecular organization and solvent dynamics in the vicinity of Lewis acid sites with differing metal site speciation remains limited. In this work, we investigate the molecular coordination and diffusion of two common solvents (methanol and water) around the closed and open Sn-BEA zeolite active sites using molecular dynamics simulations with a machine-learned interatomic potential trained on ab initio molecular dynamics trajectories. Molecular dynamics simulations reveal that introducing active sites significantly enhances local order in the first and second solvation shells compared to the pure silica case. For methanol, both closed and open active sites are singly coordinated, while more than two water molecules coordinate the open site. In contrast to methanol, we observed that water molecules dissociate, leading to the formation of additional Sn-OH and silanol groups away from the active site. The diffusion coefficients of water and methanol are functions of the solvent population in the pore. Here, our work provides insights into how active site speciation in Lewis acid zeolites affects solvent coordination, diffusion, and vibrational signature. This information is foundational for catalyst design and optimization of liquid-phase catalytic processes in zeolites. It also demonstrates the suitability of machine-learned interatomic potentials for modeling reactive systems, enabling sufficiently long trajectories for appropriate statistical averaging.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Studying f-Electron Contributions in Thorium and Uranium Containing Molecules
The pure rotational spectra of several actinide-containing compounds have been improved upon and, in two cases, been recorded for the first time. The diatomic molecules HfS and ThS have been studied in their ground electronic states but high vibrationally excited states. The results have yielded very accurate locations of the minima of the potential energy curves. The asymmetric molecules OThS and UO2S have been prepared by laser ablation synthesis and their pure rotational spectra recorded for the first time. Precise information pertinent to the geometric and electronic structure of these molecules has been obtained and is compared with other, newly recorded and related species such as OCeS.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Microwave spectrum, structure, dipole moment, and Coriolis coupling of 1,1-difluoroallene
Microwave spectra from 12.4 to 40.0 GHz were recorded for five isotopic species of 1,1-difluoroallene. A-type transitions were observed and R-branch assignments were made for the ground state and two vibrationally excited states. Several structural parameters of the compounds were determined. The dipole moment value obtained from Stark splitting was 2.07 plus or minus 0.03 D. A Coriolis coupling was observed between the two-low-frequency C = C = C bending modes.
Durig, J. R.↗
State-to-state scattering of highly vibrationally excited NO with argon at collision energies over 1 eV
State-to-state collisions of vibrationally excited NO are studied at collision energies of up to 1.4 eV.
Perera, Chatura [Department of Chemistry, Universi↗
Fourfold Clusters of Rovibrational Energies in H2Te Studied With an Ab Initio Potential Energy Function
We report an ab initio investigation of the cluster effect (i.e., the formation of nearly degenerate, four member groups of rotation-vibration energy levels at higher J and K(sub a). values) in the H2Te molecule. The potential energy function has been calculated ab initio at a total of 334 molecular geometries by means of the CCSD(T) method where the (1s-4f) core electrons of Te were described by an effective core potential. The values of the potential energy function obtained cover the region up to around 10,000/cm above the equilibrium energy. On the basis of the ab initio potential, the rotation-vibration energy spectra of H2Te-130 and its deuterated isotopomers have been calculated with the MORBID (Morse Oscillator Rigid Bender Internal Dynamics) Hamiltonian and computer program. In particular, we have calculated the rotational energy manifolds for J less than or = 40 in the vibrational ground state, the upsilon(sub 2) state, the "first triad" (the upsilon(sub l)/upsilon(sub 3)/2upsilon(sub 2) interacting vibrational states), and the "second triad" (the upsilon(sub 1) + upsilon(sub 2/upsilon(sub 2) + upsilon(sub 3)/3upsilon(sub 2) states) of H2Te-130. We find that the cluster formation in H2Te is very similar to those of of H2Se and H2S, which we have studied previously. However, contrary to semiclassical predictions, we do not determine any significant displacement of the clusters towards lower J values relative to H2Se. Hence the experimental observation of the cluster states in H2Te will be at least as difficult as in H2Se.
Jensen, Per↗
Dissociation energy and vibrational terms of ground state /X /1 Sigma g plus// hydrogen
Computations of binding energies and vibrational energies of ground state molecular hydrogen to measure accuracy of dissociation energy
Bernstein, R. B.↗
Classification and regression models of audio and vibration signals for machine state monitoring in precision machining systems
Here we present a data-driven method for monitoring machine status in manufacturing processes. Audio and vibration data from precision machining are used for inference in two operating scenarios: (a) variable machine health states (anomaly detection); and (b) settings of machine operation (state estimation). Audio and vibration signals are first processed through Fast Fourier Transform and Principal Component Analysis to extract transformed and informative features. These features are then used in the training of classification and regression models for machine state monitoring. Specifically, three classifiers (K-nearest neighbors, convolutional neural networks and support vector machines) and two regressors (support vector regression and neural network regression) were explored, in terms of their accuracy in machine state prediction. It is shown that the audio and vibration signals are sufficiently rich in information about the machine that 100% state classification accuracy could be accomplished. Data fusion was also explored, showing overall superior accuracy of data-driven regression models.
42 ENGINEERING↗
Relative intensity calculations for carbon dioxide. I - Internal partition function. II - Relative intensity of carbon dioxide lines in vibration-rotation bands arising from transitions from the ground state and from the first excited state.
Internal and vibrational partition functions of carbon dioxide and rotational line intensities arising from transitions from ground and first excited states
GROUND STATE↗
SpectrumSDT: A program for parallel calculation of coupled rotational-vibrational energies and lifetimes of bound states and scattering resonances in triatomic systems
In this work, we present SpectrumSDT – a program for calculations of energies and lifetimes of bound rotational-vibrational states below and scattering resonances above the dissociation threshold on a global potential energy surface of a triatomic system, which may include stable molecules, weekly-bound van-der-Waals complexes, and unbound atom + diatom scattering systems. Large-amplitude vibrational motion is treated explicitly using hyper-spherical coordinates. Three options for the rotational-vibrational interaction are supported: uncoupled (symmetric top rotor), partially coupled (to include interaction between several nearest states only) and full-coupled (vibrating asymmetric-top rotor). In addition to energies and lifetimes, SpectrumSDT is able to integrate ro-vibrational wave functions over the user-defined regions of potential energy surface, which helps to classify these states. In this release of the code, SpectrumSDT is limited to ABA-type molecules with wave functions that do not extend into the regions near Eckart singularities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electron collision cross sections involving excited states
The vibrational excitation/deexcitation of vibrationally and rotationally hot N2 by electron impact, pertinent to the reactions in the flow field around a hypersonic space vehicle entering the planetary atmosphere, is calculatively investigated. It is found that the resonance position shifts to a lower energy when N2 is rotationally hot. Electron impact excitations between electronic excited states of N2 are studied using a multichannel treatment. The results show that the assumption that excited-excited cross sections are the same as ground-excited ones, and result in the same final state, is invalid. A more reliable set of data on N2 is provided.
Huo, Winifred M.↗
The (FHCl)- molecular anion - Structural aspects, global surface, and vibrational eigenspectrum
State of the art ab initio electronic structure methods have been used to investigate the (FHCl)- molecular anion. It is proposed that the geometric structure and binding energies of the complex are r(e)(H-F) = 0.963 +/- 0.003 A, R(e)(H-Cl) = 1.925 +/- 0.015 A, and D0(HF + Cl(-)) = 21.8 +/- 0.4 kcal/mol. A Morokuma decomposition of the ion-molecular bonding give the following electrostatic, polarization, exchange repulsion, dispersion, and charge-transfer plus higher-order mixing components of the vibrationless complexation energy: -27.3, -5.2, +18.3, -4.5, and -5.0 kcal/mol, respectively. A couples cluster single and doubles global surface is constructed from 208 and 228 energy points for linear and bent configurations, respectively, these being fit to rms errors of only 3.9 and 9.3/cm, respectively, below 8000/cm. Converged J = 0 and J = 1 variational eigenstates of the (FHCl)- surface to near the HF + Cl(-) dissociation threshold are determined. The fundamental vibrational frequencies are found to be nu1 = 247/cm, nu2 = 876/cm, and nu3 = 2884/cm. The complete vibrational eigenspectrum is analyzed.
Klepeis, Neil E.↗
Electric dipole moment function of the X1 Sigma/+/ state of CO - Vibration-rotation matrix elements for transitions of gas laser and astrophysical interest
The electric dipole moment function of the ground electronic state of carbon monoxide has been determined by combining numerical solutions of the radial Schrodinger equation with absolute intensity data of vibration-rotation bands. The derived dipole moment function is used to calculate matrix elements of interest to stellar astronomy and of importance in the carbon monoxide laser.
Chackerian, C., Jr.↗