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Results for “Vibrational states”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping

Abstract Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can sometimes be solved by confining the liquid to an optical cavity under vibrational strong coupling conditions. For a liquid solution of 13 CO 2 solute in a 12 CO 2 solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state) of the solvent with an intense laser pulse, under suitable resonant conditions, may lead to a very strong (>3 quanta) and ultrafast (<1 ps) excitation of the solute, even though the solvent ends up being barely excited. By contrast, outside a cavity the same input pulse fluence can excite the solute by only half a vibrational quantum and the selectivity of excitation is low. Our finding is robust under different cavity volumes, which may lead to observable cavity enhancement on IR photochemical reactions in Fabry–Pérot cavities.

74 ATOMIC AND MOLECULAR PHYSICS↗
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.↗
DOE OSTI2023

Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons

This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are used to identify 1-Pyreneacetic acid as a molecule with this property and the dynamics of ESVP are modeled. Overall, this work introduces an avenue of polariton chemistry where excited state dynamics are influenced by the formation of vibrational polaritons. Along with this, the UV/vis-to-IR photonic down conversion is potentially useful in both sensing excited state vibrations and quantum transduction schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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↗
DOE OSTI2022

Structures and localized vibrational states of defects in graphite by tight-binding calculations

The structural and vibrational properties of pristine graphite and point defects in graphite are studied by tight-binding (TB) calculations using a three-center TB potential model. We showed that the three-center TB potential without ‘‘ad hoc’’ van der Waals interaction corrections can accurately describe the inter-layer distance of graphite and the lowest-energy structures and stabilities of typical point defects in graphite. The results from our TB calculations are in good agreement with those from density-functional theory calculations with van der Waals interaction corrections. We also investigated the vibrational properties to gain better understanding on the localization of vibrational states induced by the point defects. Our calculation results show that although localized or quasi-localized vibrational modes can be found in all defected graphite, the localization induced by Frenkel pair, dual-vacancy, and dual-interstitial defects is much stronger. Atomic displacements associated with the localized vibrational modes induced by these three point defects are also analyzed

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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.↗
DOE OSTI2023

Photoionization from the Ground and Excited Vibrational States of H$^+_2$ and Its Deuterated Isotopologues

Photoionization cross sections and rate coefficients have been calculated for all bound vibrational levels of the 1sσ g state of H$^+_2$, HD+, and D$^+_2$. The Born–Oppenheimer approximation is employed in our calculation of vibrationally resolved photoionization cross sections. Vibrationally resolved and local thermal equilibrium photoionization rate coefficients are presented for photon temperatures less than 50,000 K and are found to be several orders of magnitude larger than previous results in the literature. Analytic fits for the vibrationally resolved and local thermal equilibrium photoionization rate coefficients are provided. Near-threshold oscillations in the vibrationally resolved photoionization are observed. A benchmark set of photoionization cross sections are presented. Fixed-nuclei photoionization cross sections are calculated using two-center true continuum wave functions and are verified by comparison with previous calculations and are found to be in excellent agreement in all cases. Data files for our set of benchmark cross sections, rate coefficients, and fitting parameters for H$^+_2$, HD + , and D$^+_2$ are available on Zenodo under an open-source Creative Commons Attribution license at doi:10.5281/zenodo.8304061.

74 ATOMIC AND MOLECULAR PHYSICS↗
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.↗