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All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

The rotational spectrum of nitric acid - The first five vibrational states

The details of work on the nu(8) vibrational state, which arise from the NO2 out-of-plane vibration, are reported. For this state, over 210 transitions have been measured in the millimeter and submillimeter spectral region and analyzed with Watson's A-reduced centrifugal distortion Hamiltonian. Also included in this work is a comparison of all these spectra and an overview of the millimeter and submillimeter spectra associated with these states. Although at the high sensitivity available in laboratory experiments, many additional lines are observable, all arise from vibrational states whose populations are more than 100 times lower than the ground state. The most prominent of these are due to the states which give rise to the perturbed 2 nu(9) and nu(5) bands near 11 microns. These results provide a significant data base for both atmospheric remote sensing experiments and spectral analyses of data in other spectral regions, especially the IR.

Crownover, Richard L.↗
NASA NTRS2020

Propionitrile in the Two Lowest Excited Vibrational States in the Laboratory and on Titan

The rotational spectrum of propionitrile (ethyl cyanide, C2H5CN) in the two lowest excited vibrational states, ν(sub 13) = 1 and ν(sub 21) = 1, was studied in detail. The compiled experimental data set consisted of published line lists, lines measured from published spectra up to 645 GHz, and new measurements at frequencies from 8 to 331 GHz. The two states are subject to considerable mutual interaction but application of a- and b-axis Coriolis coupling model to the measured A-symmetry internal rotation substate transitions was found to be successful. A total of over 1900 transitions were fitted for J values up to 76 and Ka up to 24, resulting in determined vibrational separation between the two states ΔE = 6:2070246(14) cm(exp -1), and Coriolis coefficients |ζ(sup a)(sub 13,21)| = 0.378, |ζ(sup b) (sub 13,21)| = 0.127, in good agreement with quantum chemistry calculations. The new line catalog was used to model ALMA spectra of Titan’s atmosphere from 2016, fitting many weak lines not previously modeled. By including the vibrationally excited lines of C2H5CN and a new partition function, we derive a disk-averaged volume mixing ratio estimate in 2016 of 7.8 ± 0.2 ppb assumed constant above 300 km.

Analysis of rotational spectrum↗
NASA NTRS1995

A FFT Method for the Quasiclassical Selection of Initial Ro-Vibrational States of Triatomic Molecules

This paper describes the use of an exact fast Fourier transform (FFT) method to prepare specified vibrational-rotational states of triatomic molecules. The method determines the Fourier coefficients needed to describe the coordinates and momenta of a vibrating-rotating triatomic molecule. Once the Fourier coefficients of a particular state are determined, it is possible to easily generate as many random sets of initial cartesian coordinates and momenta as desired. All the members of each set will correspond to the particular vibrational-rotational state selected. For example, in the case of the ground vibrational state of a non-rotating water molecule, the calculated actions of 100 sets of initial conditions produced actions within 0.001 h(bar) of the specified quantization values and energies within 5 cm(sup -1) of the semiclassical eigenvalue. The numerical procedure is straightforward for states in which all the fundamental frequencies are independent. However for states for which the fundamental frequencies become commensurate (resonance states), there are additional complications. In these cases it is necessary to determine a new set of "fundamental" frequencies and to modify the quantization conditions. Once these adjustments are made, good results are obtained for resonance states. The major problems are in labelling the large number of Fourier coefficients and the presence of regions of chaotic motion. Results are presented for the vibrational states of H2O and HCN and the ro-vibrational states of H2O.

Eaker, Charles W.↗
NASA NTRS2001

Ab Initio and Improved Empirical Potentials for the Calculation of the Anharmonic Vibrational States and Intramolecular Mode Coupling of N-Methylacetamide

The second-order Moller-Plesset ab initio electronic structure method is used to compute points for the anharmonic mode-coupled potential energy surface of N-methylacetamide (NMA) in the trans(sub ct) configuration, including all degrees of freedom. The vibrational states and the spectroscopy are directly computed from this potential surface using the Correlation Corrected Vibrational Self-Consistent Field (CC-VSCF) method. The results are compared with CC-VSCF calculations using both the standard and improved empirical Amber-like force fields and available low temperature experimental matrix data. Analysis of our calculated spectroscopic results show that: (1) The excellent agreement between the ab initio CC-VSCF calculated frequencies and the experimental data suggest that the computed anharmonic potentials for N-methylacetamide are of a very high quality; (2) For most transitions, the vibrational frequencies obtained from the ab initio CC-VSCF method are superior to those obtained using the empirical CC-VSCF methods, when compared with experimental data. However, the improved empirical force field yields better agreement with the experimental frequencies as compared with a standard AMBER-type force field; (3) The empirical force field in particular overestimates anharmonic couplings for the amide-2 mode, the methyl asymmetric bending modes, the out-of-plane methyl bending modes, and the methyl distortions; (4) Disagreement between the ab initio and empirical anharmonic couplings is greater than the disagreement between the frequencies, and thus the anharmonic part of the empirical potential seems to be less accurate than the harmonic contribution;and (5) Both the empirical and ab initio CC-VSCF calculations predict a negligible anharmonic coupling between the amide-1 and other internal modes. The implication of this is that the intramolecular energy flow between the amide-1 and the other internal modes may be smaller than anticipated. These results may have important implications for the anharmonic force fields of peptides, for which N-methylacetamide is a model.

Gregurick, Susan K.↗
NASA NTRS1995

Molecular vibrational states during a collision

Alternative algebraic techniques to approximate a given Hamiltonian by a harmonic oscillator are described both for time-independent and time-dependent systems. We apply them to the description of a one dimensional atom-diatom collision. From the resulting evolution operator, we evaluate vibrational transition probabilities as well as other time-dependent properties. As expected, the ground vibrational state becomes a squeezed state during the collision.

Recamier, Jose A.↗
NASA NTRS1987

Picosecond excite-and-probe absorption measurement of the intra-2E(g)E(3/2)-state vibrational relaxation time in Ti(3+):Al2O3

The Ti(3+)-doped Al2O3 has been recently demonstrated to be a tunable solid-state laser system with Ti(3+) as the laser-active ion. In this paper, the kinetics of vibrational transitions in the 2E(g)E(3/2) electronic state of Ti(3+):Al2O3a (crucial for characterizing new host materials for the Ti ion) was investigated. A 527-nm 5-ps pulse was used to excite a band of higher vibrational levels of the 2E(g)E(3/2) state, and the subsequent growth of population in the zero vibrational level and lower vibrational levels was monitored by a 3.9-micron picosecond probe pulse. The time evolution curve in the excited 2E(g)E(3/2) state at room temperature was found to be characterized by a sharp rise followed by a long decay, the long lifetime decay reflecting the depopulation of the zero and the lower vibrational levels of the 2E(g)E(3/2) state via radiative transitions. An upper limit of 3.5 ps was estimated for intra-2E(g)E(3/2)-state vibrational relaxation time.

Gayen, S. K.↗
NASA NTRS1984

VIBRA: An interactive computer program for steady-state vibration response analysis of linear damped structures

An interactive steady state frequency response computer program with graphics is documented. Single or multiple forces may be applied to the structure using a modal superposition approach to calculate response. The method can be reapplied to linear, proportionally damped structures in which the damping may be viscous or structural. The theoretical approach and program organization are described. Example problems, user instructions, and a sample interactive session are given to demonstate the program's capability in solving a variety of problems.

Bowman, L. M.↗
NASA NTRS1993

The nu(sub 2) and 2nu(sub 2) - nu(sub 2) bands of N-14 (16)O2: Electron Spin-Rotation and Hyperfine Contact Resonances in the (010) Vibrational State

High-resolution Fourier transform spectra covering the 720-9-10/ cm spectral region have been used to perform a reanalysis of the 2nu(sub 2) band ((010) - (000) vibrational transition) together with the first analysis of the nu(sub 2) - nu(sub 2) hot band of nitrogen dioxide ((020)-(010) vibrational transition). The high-quality spectra show that, for numerous nu(sub 2) lines, the hyperfine structure is easily observable in the case of resonances due to the hyperfine Fermi-type operator. By performing a full treatment of the spin-rotation and of the hyperfine operators, a near line list of the nu(sub 2) band (positions and intensities) has been generated, and it is in excellent agreement with the experimental spectrum. Also, a thorough analysis of the -2nu(sub 2) nu(sub 2) hot band has been performed leading to an extended set of new (020) spin-rotation levels, These levels, together with the (100), (020), (001) spin-rotation levels deduced previously from the analysis of thenu(sub 1), 2nu(sub 2), and nu(sub 3) cold bands performed in the 6.3 - to 7.5 microns spectral range were least-squares fitted, allowing one to derive a new set of vibrational band centers and rotational. spin-rotation, and interaction constants for the {(100)(020)(001)} interacting states of N-14(16)O2.

Perrin, A.↗
NASA NTRS1992

Relaxation of higher vibrational states in diatomic gases

A general and computationally efficient approach evaluating the transition probabilities for the V-T exchange, involving highly excited levels and the transitions of delta-v of more than 1, in diatomic gases is presented. The role of the repulsive part of the intermolecular potential on the transition probability is also investigated. Examples of numerical results are given for number of transitions in nitrogen and oxygen molecules in the ground electronic states. The approach can be used for interactions involving diatomic molecular ions.

Kunc, J. A.↗
NASA NTRS1981

Design and evaluation of a state-feedback vibration controller

The effectiveness and practicality of the state-feedback vibration controller is demonstrated by computer simulations. It is shown that: (1) the required measurements can be reduced to fuselage accelerations; (2) the system is stable over a wide range of flight conditions; (3) a discrete design for the controller provides effective digital implementation at 80-Hz sampling; (4) attenuation produced by the actuators does not create a problem, and a simple lead compensator provides vibration reduction; and (5) a design based on a hover model worked well at five knots. At 40 and 120 knots, vibrations in all but the vertical acceleration were effectively suppressed. The state-feedback vibration controller has a rapid convergence time and implementation is easier than with multicyclic control since no on-line harmonic analysis or identification algorithms are required.

Du Val, R. W.↗
NASA NTRS1988

The rate parameters for coupled vibration-dissociation in a generalized SSH approximation

A theoretical study of vibrational excitations and dissociations of nitrogen undergoing a nonequilibrium relaxation process upon heating and cooling is reported. The rate coefficients for collisional induced vibrational transitions and transitions from a bound vibrational state into a dissociative state have been calculated using an extension of the theory originally proposed by Schwarz (SSH) et al. (1952). High-lying vibrational states and dissociative states were explicitly included but rotational energy transfer was neglected. The transition probabilities calculated from the SSH theory were fed into the master equation, which was integrated numerically to determine the population distribution of the vibrational states as well as bulk thermodynamic properties. The results show that: (1) the transition rates have a minimum near the middle of the bound vibrational levels, causing a bottleneck in the vibrational relaxation and dissociation rates; (2) high vibrational states are always in equilibrium with the dissociative state; (3) for the heating case, only the low vibrational states relax according to the Landau-Teller theory; (4) for the cooling case, vibrational relaxation cannot be described by a rate equation; (5) Park's (1985, 1988) two-temperature model is approximately valid; and (6) the average vibrational energy removed in dissociation is about 30 percent of the dissociation energy.

Sharma, Surendra P.↗
NASA NTRS1988

Line positions and intensities for the gamma 1 + gamma 2 and gamma 2 + gamma 3 bands of (16)O3

Using 0.005 cm-resolution Fourier transform spectra of (16)O3, generated by electric discharge from a greater than 99.98 percent pure sample of (16)O3, an extensive analysis of the gamma 1 + gamma 2 and the gamma 2 + gamma 3 bands in the 5.7 micron region was performed. The rotational energy levels of the upper (110) and (011) vibrational states of (16)O3 were reproduced within their experimental uncertainties using a Hamiltonian which takes explicitly into account the Coriolis-type interaction occurring between the rotational energy levels of both states. Improved vibrational energies and rotational and coupling constants were also derived for the (110) and (011) states. Precise transition moment constants for these two bands were deduced from analysis of 220 measured line intensities. Finally, a complete list of line positions, intensities, and lower state energies for both bands has been generated.

Devi, V. Malathy↗
NASA NTRS1991

A coupled channel study of HN2 unimolecular decay based on a global ab initio potential surface

The unimolecular decay lifetimes of several vibrational states of HN2 are determined on the basis of an accurate coupled channel dynamics study using a global analytical potential surface. The surface reproduces the ab initio points with an rms error of 0.08 kcal/mol for energies below 20 kcal/mol. Modifications to the potential that describe the effect of improving the basis set in the ab initio calculations are provided. Converged coupled channel calculations are performed for the ground rotational state of HN2 to determine the lifetimes of the lowest ten vibrational states. Only the ground vibrational state (000) and first excited bend (001) are found to have lifetimes longer than 1 ps. The lifetimes of these states are estimated at 3 x 10 to the -9th and 2 x 10 to the -10th s, respectively. Variation of these results with quality of the ab initio calculations is not more than a factor of 5.

Koizumi, Hiroyasu↗
NASA NTRS1976

Vibration-translation energy transfer in vibrationally excited diatomic molecules

A semiclassical collision model is applied to the study of energy transfer rates between a vibrationally excited diatomic molecule and a structureless atom. The molecule is modeled as an anharmonic oscillator with a multitude of dynamically coupled vibrational states. Three main aspects in the prediction of vibrational energy transfer rates are considered. The applicability of the semiclassical model to an anharmonic oscillator is first evaluated for collinear encounters. Second, the collinear semiclassical model is applied to obtain numerical predictions of the vibrational energy transfer rate dependence on the initial vibrational state quantum number. Thermally averaged vibration-translation rate coefficients are predicted and compared with CO-He experimental values for both ground and excited initial states. The numerical model is also used as a basis for evaluating several less complete but analytic models. Third, the role of rational motion in the dynamics of vibrational energy transfer is examined. A three-dimensional semiclassical collision model is constructed with coupled rotational motion included. Energy transfer within the molecule is shown to be dominated by vibration-rotation transitions with small changes in angular momentum. The rates of vibrational energy transfer in molecules with rational frequencies that are very small in comparison to their vibrational frequency are shown to be adequately treated by the preceding collinear models.

Mckenzie, R. L.↗