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Results for “MOLECULAR ROTATION”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

On the use of stereodynamical effects to control cold chemical reactions: The H + D 2 ↔ D + HD case study

Here, quantum calculations are reported for the stereodynamic control of the H + D 2 ↔ D + HD chemical reaction in the energy range of 1–50 K. Stereodynamic control is achieved by a formalism similar to that reported by Perreault et al. [Nat. Chem. 10, 561 (2018)] in recent experimental works in which the alignment of the molecular bond axis relative to the incident relative velocity is controlled by selective preparations of the molecule in a specific or superposition of magnetic projection quantum numbers of the initial molecular rotational level. The approach presented here generalizes the experimental scheme of Perreault et al. and offers additional degree of control through various experimental preparations of the molecular alignment angle. Illustrative results presented for the H + D 2 and D + HD reactions show significant control with the possibility of turning the reaction completely on or off with the appropriate stereodynamic preparation of the molecular state. Various scenarios for maximizing and minimizing the reaction outcomes are identified with the selective preparation of molecular rotational states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Rotation in attosecond vibronic coherence spectroscopy for molecules

Abstract Excitation or ionization of a molecule by ultrafast laser pulses can create a superposition of electronic states, whose dynamics is influenced by the interplay of electronic coherence and nuclear motion, resulting in charge migration and possibly charge transfer. Probing the vibronic coherence is therefore vital to monitoring electronic dynamics and controlling chemical reactivity, as recently demonstrated in molecules via attosecond transient absorption spectroscopy (ATAS). However, theories supporting the interpretation of ATAS experiments neglect the effects of molecular rotation, often leading to inaccurate interpretation of experimental data. Here, we develop a comprehensive theory for ATAS of molecules encompassing the entire pump-probe process. Applying the theory to N 2 , we demonstrate that the emergence of coherent signals critically depends on the consideration of molecular rotation. This work contributes to close the gap between theory and ATAS experiments, paving the way for monitoring electronic motion and controlling chemical reactivity in diverse molecular systems.

Physics↗
NASA NTRS1979

Detection of the 12.28 micron rotational line of molecular hydrogen in the Orion molecular cloud

The pure rotational S(2) transition of molecular hydrogen at 12.28 microns has been detected in emission from the region of vibrational-rotational line emission in Orion. The line was resolved both spectrally and spatially, and the line shapes, widths, and velocities are consistent with those observed in the upsilon = 1-0 transitions. The results put new constraints on the structure, temperature, and dynamics of the region of molecular hydrogen emission.

Beck, S. C.↗
DOE OSTI2025

Conveyor-belt magneto-optical trapping of molecules

Abstract Laser cooling is used to produce ultracold atoms and molecules for quantum science and precision measurement applications. Molecules are more challenging to cool than atoms due to their vibrational and rotational internal degrees of freedom. Molecular rotations lead to the use of type-II transitions ( F ⩾ F ′ ) for magneto-optical trapping (MOT). When typical red detuned light frequencies are applied to these transitions, sub-Doppler heating is induced, resulting in higher temperatures and larger molecular cloud sizes than realized with the type-I MOTs most often used with atoms. To improve type-II MOTs, Jarvis et al (2018 Phys. Rev. Lett. 120 083201) proposed a blue-detuned MOT to be applied after initial cooling and capture with a red-detuned MOT. This was successfully implemented (Burau et al 2023 Phys. Rev. Lett. 130 193401; Jorapur et al 2024 Phys. Rev. Lett. 132 163403; Li et al 2024 Phys. Rev. Lett. 132 233402), realizing colder and denser molecular samples. Very recently, Hallas et al (2024 arXiv:2404.03636) demonstrated a blue-detuned MOT with a ‘1+2’ configuration that resulted in even stronger compression of the molecular cloud. Here, we describe and characterize theoretically the conveyor-belt mechanism that underlies this observed enhanced compression. We perform numerical simulations of the conveyor-belt mechanism using both stochastic Schrödinger equation and optical Bloch equation approaches. We investigate the conveyor-belt MOT characteristics in relation to laser parameters, g -factors and the structure of the molecule, and find that conveyor-belt trapping should be applicable to a wide range of laser-coolable molecules.

Li, Grace K. (ORCID:0000000277223355)↗
NASA NTRS1989

The rate parameters for coupled rotation-vibration-dissociation phenomenon in H2

The effects of molecular rotation on coupled vibration-dissociation phenomena in H2 undergoing a nonequilibrium relaxation in a heating and cooling environment were studied theoretically. The rate coefficients for the collisional bound-bound and bound-free transitions, calculated by a quasi-classical trajectory method, were fed into the master equation, which was numerically solved to determine the rotational and vibrational population densities and bulk thermodynamic properties. Results indicate that the vibrational transition rates of H2 increase monotonically with the vibrational levels, faster than in the Landau-Teller (1936) model, and that the rotation of the molecules helps relax the low vibrational levels, serves as a temporary storage of vibrational energy during the relaxation, and thereby delays the dissociation process. The average energy loss due to the dissociation was determined to be about 80-90 percent of the total dissociation energy.

Sharma, Surendra P.↗
NASA NTRS1987

Assessment of two-temperature kinetic model for ionizing air

A two-temperature chemical-kinetic model for air is assessed by comparing theoretical results with existing experimental data obtained in shock-tubes, ballistic ranges, and flight experiments. In the model, named the TTv model, one temperature (T) is assumed to characterize the heavy-particle translational and molecular rotational energies, and another temperature (Tv) to characterize the molecular vibrational, electron translational, and electronic excitation energies. The theoretical results for nonequilibrium air flow in shock tubes are obtained using the computer code STRAP (Shock-Tube Radiation Program), and for flow along the stagnation streamline in the shock layer over spherical bodies using the newly developed code STRAP (Stagnation-Point Radiation Program). Substantial agreement is shown between the theoretical and experimental results for relaxation times and radiative heat fluxes. At very high temperatures the spectral calculations need further improvement. The present agreement provides strong evidence that the two-temperature model characterizes principal features of nonequilibrium air flow. New theoretical results using the model are presented for the radiative heat fluxes at the stagnation point of a 6-m-radius sphere, representing an aeroassisted orbital transfer vehicle, over a range of free-stream conditions. Assumptions, approximations, and limitations of the model are discussed.

Park, Chul↗
DOE OSTI2024

Bulk viscosity of the rigid rotor one-component plasma

Bulk viscosity of a plasma consisting of strongly coupled diatomic ions is computed using molecular dynamics simulations. The simulations are based on the rigid rotor one-component plasma, which is introduced as a model system that adds two degrees of molecular rotation to the traditional one-component plasma. It is characterized by two parameters: the Coulomb coupling parameter, Γ, and the bond length parameter, Ω. Results show that the long-range nature of the Coulomb potential can lead to long rotational relaxation times, which in turn yield large values for bulk viscosity. Here, the bulk-to-shear viscosity ratio is found to span from small to large values depending on the values of Γ and Ω. Although bulk viscosity is often neglected in plasma modeling, these results motivate that it can be large in molecular plasmas with rotational degrees of freedom.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1994

Rotational relaxation of molecular hydrogen at moderate temperatures

Using a coupled rotation-vibration-dissociation model the rotational relaxation times for molecular hydrogen as a function of final temperature (500-5000 K), in a hypothetical scenario of sudden compression, are computed. The theoretical model is based on a master equation solver. The bound-bound and bound-free transition rates have been computed using a quasiclassical trajectory method. A review of the available experimental data on the rotational relaxation of hydrogen is presented, with a critical overview of the method of measurements and data reduction, including the sources of errors. These experimental data are then compared with the computed results.

COUPLED ROTATION VIBRATION DIS↗
DOE OSTI2023

Extragalactic CO emission lines in the CMB experiments: A forgotten signal and a foreground

High resolution cosmic microwave background (CMB) experiments have allowed us to precisely measure the CMB temperature power spectrum down to very small scales (multipole ℓ ~ 3000). Such measurements at multiple frequencies enable separating the power spectrum of the primary CMB anisotropies with the power spectrum of other signals like CMB lensing, thermal and kinematic Sunyaev-Zel’dovich effects (tSZ and kSZ), and cosmic infrared background (CIB). Here, in this paper, we explore another signal of interest at these frequencies that should be present in the CMB maps: extragalactic CO molecular rotational line emissions, which are the most widely used tracers of molecular gas in the line intensity mapping experiments. Using the SIDES simulations adopted for top hat bandpasses at 150 and 220 GHz, we show that the cross-correlation of the CIB with CO lines has a contribution similar to the CIB-tSZ correlation and the kSZ power, thereby contributing a non-negligible amount to the total power at these scales. This signal, therefore, may significantly impact the recently reported ≥3σ detection of the kSZ power spectrum from the South Pole Telescope collaboration, as the contribution of the CO lines is not considered in such analyses. Our results also provide a new way of measuring the CO power spectrum in cross-correlation with the CIB. Finally, these results show that the CO emissions present in the CMB maps will have to be accounted for in all the CMB auto-power spectrum and cross-correlation studies involving a large-scale structure tracer.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1995

Rotational And Rovibrational Energy Transfer In Electron Collisions With Molecules

Air flows around a hypervelocity reentry vehicle undergo dissociation, rovibrational excitation and ionization. More specifically the air, initially 80% N2 and 20% O2, in the shock layer consists of species such as N, O, N2, O2, NO, N+, O+, N+, O+, NO+ and 2 free electrons. It was pointed out in multi temperature models'' that the temperature of the rotational energy modes and the gas-kinetic translational temperature are quickly equilibrated by a few collisions and rise rapidly to high temperatures as 50000K before falling off to equilibrium value of 10000K. Contrary, the electronic and vibrational temperatures state energy distributions remain low (less than 15000K) because of the slow equilibration. Electron vibrational energy transfer is thought to play a crucial role in such a ionizing flow regime since chemical reaction rates and dissociation depend strongly on the vibrational temperatures. Modeling of these flowfields in principle require the rovibrational excitation and de-excitation cross section data for average electron energies from threshold up to several eV (leV=11605.4 K). In this lecture we focus on theoretical description of rotational effects i.e. energy transfer of electrons to molecules such that the molecular rotational (vojo goes to voj) or vibrational and rotational (v(sub 0)j(sub 0) goes to vj) states are changed. Excitation and de-excitation of electronic states was discussed in a previous talk at this conference.

Thuemmel, Helmar T.↗
NASA NTRS1992

Rotational relaxation of molecular H2 at moderate temperatures

A coupled rotation-vibration-dissociation model is used to compute the rotational relaxation times for molecular hydrogen as a function of final temperatures (500-5000 K) in a hypothetical scenario of sudden compression. The theoretical model is based on a master equation solver. The bound-bound and bound-free transition rates have been computed using a quasi-classical trajectory method. A review of the available experimental data on the rotational relaxation of hydrogen is presented, with a critical overview of the method of measurements and data reduction, including the sources of errors. The experimental data are compared with the computed results.

Sharma, S. P.↗
DOE OSTI2025

Real-Space Local Dynamics in 1,2,3-Triazole Using Inelastic Neutron Scattering

Enhancing proton transport in polymer electrolytes is crucial for advancing next-generation solid-state batteries, yet our understanding of proton conductivity in nonaqueous environments remains limited due to a lack of atomic-scale insights. Here, in this study, we investigated the atomic-scale dynamics of 1,2,3-triazole, a small molecule capable of dynamic hydrogen bonding, as a model system for proton hopping in nonaqueous environments. Using the real-space correlation function determined by the double Fourier transformation of inelastic neutron scattering spectra, we identified that the self-motion of protons and intermolecular dynamics occur on comparable time scales. Furthermore, we observed that the activation energy associated with the intermolecular dynamics matches the energy barrier for molecular rotations determined through Density Functional Theory calculations. These findings underscore the importance of controlling molecular dynamics at the atomic scale to control proton transport. Additionally, we demonstrated that intermolecular dynamics in systems involving protons can be studied using inelastic neutron scattering even without deuteration, thereby providing a broader avenue for studying atomic-scale dynamics in soft matter systems.

Shinohara, Yuya [Oak Ridge National Laboratory (OR↗
NASA NTRS1991

Effect of the rotational-vibrational excitation on molecular diameters

The kinetic molecular diameters of rotationally and vibrationally excited diatomic molecules and molecular ions are derived as functions of the rotational and vibrational quantum numbers of the molecules. Typical molecular diameters are studied in two cases: in low-temperature gas, where the molecular diameter is independent of the degree of rotational-vibrational excitation of the molecules, and in high-temperature gas, where the molecular diameter depends on the degree of rotational-vibrational excitation of the molecules. The rotational-vibrational excitation of molecules is shown to have a meaningful effect on the collisional properties of gases. The effect is stronger in gases of weakly-bound molecules.

Kang, S. H.↗
NASA NTRS1960

Slow-Neutron Scattering by Rotators. II

The methods developed in a previous paper for extending the neutron scattering formalism of Zemach and Glauber to any type of molecular rotator have been employed to derive generalized forms generalized forms of the differential cross sections for rotator scattering. A mass-ratio expansion for the treatment of the high-energy limit is illustrated on the classical cross section and then employed in the treatment of the more general quantum-mechanical expression for the differential cross section. The results apply to an arbitrarily asymmetric rotator. The very low energy approximation is carried out for the symmetric rotator, and the procedure is compared with the explicit summing of the partial cross sections for individual rotational transitions. The inelastic correction to the static approximation for interference scattering is calculated to an accuracy of first order in the mass ratios for the case of the symmetric rotator.

Volkin, Howard C.↗
NASA NTRS1997

Molecular Infrared Intensity Standards

Molecular rotational and vibration-rotation spectroscopy can be a powerful tool for determining abundances and physical conditions in gases over a wide range of molecular abundance, temperature and to some extent pressure. In this paper I discuss experimental requirements for obtaining absolute intensity standards for stable molecules as well as radical molecular species. I also review the application of absolute and relative molecular intensity information for determining "conditions" in equilibrium and non-equilibrium gases.

Chackerian, C.↗