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NASA NTRS1965

Theory of Intramolecular Relaxation Processes

A master equation is derived to describe internal relaxation processes in molecular systems with a relatively small number of degrees of freedom. It is an inhomogeneous equation, taking into account nondiagonal elements of the coarse‐grained density matrix which prove to be the most relevant ones for the problem under consideration. Various relaxational time scales, inherent in a molecular system, can thus be shown to exist. Relaxation mechanisms and equilibrium states on these time scales can be determined. The general character and different types of solutions of the master equation are investigated. The theory is applied to internal vibrational relaxation and intramolecular rearrangement (isomerization) reactions.

Hofacker, G. Ludwig↗

NASA NTRS1994

Rotational Relaxation Analysis of Nitrogen in Low-Density Freejet Expansions

The phenomena of rotational relaxation of nitrogen has been examined by numerous investigators over many years. One of the experiments which has been performed examines nonequilibrium flow in low-density free jet expansions. Data have been taken in such flows using a variety of techniques, including time-of-flight methods and electron beam fluorescence spectroscopy. The direct flow properties measured in these different investigations, such as density and translational, rotational and vibrational temperatures generally show reasonable agreement. However, this kind of correlation from experiment to experiment tends to be lost when these data are analyzed to obtain rotational relaxation time or collision number. The goal of such data analyses is to generate a succinct model for rotational relaxation in nitrogen which is essential for the computation of nonequilibrium rarefied flows. The objective of the present work is to process a large body of experimental data in a consistent manner to yield relaxation model parameters of the greatest utility for flow computations.

Gochberg, Lawrence A.↗

DOE OSTI2020

Reversible structural transformations in supercooled liquid water from 135 to 245 K

Water has many anomalous properties compared to “simple” liquids, and these anomalies are typically enhanced in supercooled water.1-3 While numerous models have been proposed, including the liquid-liquid critical point,4,5 the singularity-free scenario,6 and the stability limit conjecture,1 a molecular-level understanding remains elusive. The main difficulty in determining which, if any, of these models is correct is the limited amount of data in the relevant temperature and pressure ranges. For water at ambient pressures, which is the focus of this work, data is largely missing from 160 – 232 K (“No Man’s Land”) due to rapid crystallization.2,3 Whether rapid crystallization is just an experimental obstacle, or a fundamental problem signaling the inability of water to thermally equilibrate prior to crystallization is also a major unanswered question.5,7 Here, we investigate the structural transformations of transiently-heated, supercooled water with nanosecond time resolution using infrared vibrational spectroscopy. The experiments demonstrate three key results. First, water’s structure relaxes from its initial configuration to a “steady-state” configuration prior to the onset of crystallization over a wide temperature range. Second, water’s steady-state structure can be reproduced by a linear combination of two, temperature-independent structures that correspond to a “high-temperature liquid” and a “low-temperature liquid.” Third, the observed structural changes are reversible over the full temperature range. Taken together, these results show that supercooled water can equilibrate prior to crystallization for temperatures from the homogeneous nucleation temperature, TH ~232 K,3 down to the glass transition temperature (Tg ~ 136 K). Second, the results provide support for the hypothesis that supercooled water can be described as a mixture of two, structurally-distinct, interconvertible liquids from 135 K to 245 K.5,8-18

Kringle, Loni M.↗

DOE OSTI2021

Complex Formation and Dissociation Dynamics on Amorphous Silica Surfaces

Benzene complex formation and dissociation dynamics with silanols on the amorphous silica surfaces of nanoporous SiO 2 , from a benzene/carbon tetrachloride solution, were measured by the growth of off-diagonal peaks in the two dimensional infrared (2D IR) chemical exchange spectrum of the isolated Si-OD stretch. The presence of two types of isolated silanols, referred to as type I and II, was revealed, with dissociation time constants of 82 ps and 4.0 ps for type I and II complexes, respectively. The type I silanols are associated with the main IR absorption feature in the Si-OD stretching region, while the type II silanols give rise to a broader shoulder to lower frequency. Polarization selective pump-probe (PSPP) measurements provided the vibrational lifetimes and orientational relaxation rates of the two silanols in the CCl 4 (free) and benzene (complex) environments. The type II silanols constitute roughly 30% of the isolated silanol population and exhibit a substantially faster rate of vibrational relaxation, making the type I dynamics the dominant contribution to the PSPP and 2D IR signals. From the measured dissociation times, the enthalpies of formation for the two surface complexes were obtained; the formation of the type I complex being significantly more exothermic. Furthermore, as the type II site is preferentially removed from the amorphous silica surface with increasing activation temperature, the results provide a reasonable explanation for the increased exothermicity of benzene adsorption on silica with increasing activation temperature in previous calorimetry experiments.

14 SOLAR ENERGY↗

DOE OSTI2020

Ultrafast vibrational dynamics of a trigonal planar anionic probe in ionic liquids (ILs): A two-dimensional infrared (2DIR) spectroscopic investigation

A major impediment limiting the widespread application of ionic liquids (ILs) is their high shear viscosity. Incorporation of a tricyanomethanide (TCM - ) anion in ILs leads to low shear viscosity and improvement of several characteristics suitable for large scale applications. However, properties including interactions of TCM - with the local environment and dynamics of TCM - have not been thoroughly investigated. Herein, we have studied the ultrafast dynamics of TCM - in several imidazolium ILs using linear IR and two-dimensional infrared spectroscopy techniques. The spectral diffusion dynamics of the CN stretching modes of TCM - in all ILs exhibit a nonexponential behavior with a short time component of ~2 ps and a long time component spanning ~9 ps to 14 ps. The TCM - vibrational probe reports a significantly faster relaxation of ILs compared to those observed previously using linear vibrational probes, such as thiocyanate and selenocyanate. Our results indicate a rapid relaxation of the local ion-cage structure embedding the vibrational probe in the ILs. The faster relaxation suggests that the lifetime of the local ion-cage structure decreases in the presence of TCM - in the ILs. Linear IR spectroscopic results show that the hydrogen-bonding interaction between TCM - and imidazolium cations in ILs is much weaker. Shorter ion-cage lifetimes together with weaker hydrogen-bonding interactions account for the low shear viscosity of TCM - based ILs compared to commonly used ILs. In addition, this work demonstrates that TCM - can be used as a potential vibrational reporter to study the structure and dynamics of ILs and other molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1988

Computations of unsteady dissociating nitrogen flows

A time-accurate computer program has been developed to solve flows involving nonequilibrium chemical reactions and vibrational relaxation. The program is based on a multidomain approach and an explicit MacCormack scheme. Results are presented for three simple test cases, involving nitrogen dissociation in a closed box.

Marraffa, Lionel↗

DOE OSTI2026

Experimental Quantification of Spin–Phonon Coupling in Molecular Qubits Using Inelastic Neutron Scattering

Electronic spin superposition states enable nanoscale sensing through their sensitivity to the local environment, yet their sensitivity to vibrational motion also limits their coherence times. In molecular spin systems, chemical tunability and atomicscale resolution are accompanied by a dense, thermally accessible phonon spectrum that introduces efficient spin relaxation pathways. Despite extensive theoretical work, there is little experimental consensus on which vibrational energies dominate spin relaxation or how molecular structure controls spin−phonon coupling (SPC). We present a fully experimental method to quantify SPC coefficients by combining temperature-dependent vibrational spectra from inelastic neutron scattering with spin relaxation rates measured by electron paramagnetic resonance. We apply this framework to two model S = 1/2 systems, copper(II) phthalocyanine (CuPc) and copper(II) octaethylporphyrin (CuOEP). Two distinct relaxation regimes emerge: below 40 K, weakly coupled lattice modes below 50 cm −1 dominate, whereas above 40 K, optical phonons above ∼185 cm −1 become thermally populated and drive relaxation with SPC coefficients nearly 3 orders of magnitude larger. Structural distortions in CuOEP that break planar symmetry soften the crystal lattice and enhance anharmonic scattering but also raise the energy of stretching modes at the molecular core where the spins reside. This redistributes vibrational energy toward the molecular periphery and out of plane, ultimately reducing SPC relative to CuPc and enabling room-temperature spin coherence in CuOEP. Although our method does not provide mode-specific SPC coefficients, it quantifies contributions from distinct spectral regions and establishes a broadly applicable, fully experimental link between crystal structure, lattice dynamics, and spin relaxation.

Lohaus, Stefan H. [California Institute of Technol↗

NASA NTRS1999

Inspection of Space Station Cold Plate Using Visual and Automated Holographic Techniques

Real-time holography has been used to confirm the presence of non-uniformity in the construction of an International Space Station cold plate. Ultrasonic C-scans have previously shown suspected areas of cooling fin disbonds. But both neural-net processed and visual holography did not evidence any progressive permanent changes resulting from 3000 pressurization and relaxation cycles of a Dash 8 cold plate. Neural-net and visual inspections were performed of characteristic patterns generated from electronic time-average holograms of the vibrating cold plate. Normal modes of vibration were excited at very low amplitudes for this purpose, The neural nets were trained to flag very small changes in the mode shapes as encoded in the characteristic patterns. Both the whole cold plate and a zoomed region were inspected. The inspections were conducted before, after, and during pressurization and relaxation cycles of the cold plate. A water-filled cold plate was pressurized to 120 psig (827 kPa) and relaxed for each cycle. Each cycle required 5 seconds. Both the artificial neural networks and the inspectors were unable to detect changes in the mode shapes of the relaxed cold plate. The cold plate was also inspected visually using real-time holography and double-exposure holography. Regions of non-uniformity correlating with the C-scans were apparent, but the interference patterns did not change after 3000 pressurization and relaxation cycles. These tests constituted the first practical application of a neural-net inspection technique developed originally with support from the Director's Discretionary Fund at the Glenn Research Center at Lewis Field.

Decker, Arthur J.↗

DOE OSTI2021

Slow spin relaxation in single endohedral fullerene molecules

Well-protected magnetization, tunable quantum states, and long spin-relaxation time are desired for the use of magnetic molecules in spintronics and quantum information technologies. In this work, endohedral fullerene molecules M@C 28 with different transition-metal cores were explored through systematic first-principles calculations and spin dynamics analyses. Many of them have bias-tunable structure, stable magnetization, and sizable magnetic anisotropy energy. Furthermore, some of them may have spin-relaxation time up to several milliseconds for their quantum spin states at high temperature (~10 K) after full consideration of spin-vibration couplings. In conclusion, our results suggest that these M@C 28 provide a rich pool of single-molecule magnets for diverse applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Abnormal Slow Phonon Dynamics Toward Prolonging Excited States Dynamics Enabled by Crystalline‐Assembling Donor–Acceptor Molecules

Phonon dynamics are a critical factor to control the optical properties of excited states in light-emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor-acceptor (D–A) molecules [2-(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation-modulated Raman spectroscopy, we find that the crystalline-lattice vibrations monitored by Raman-scattering laser beam of 785 nm demonstrate an un-usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline-assembling the D–A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline-assembling the D–A molecules into dipolar crystal. Here, this hypothesis can be verified by directly suppressing the phonon dynamics through freezing D–A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s- after removing photoexcitation. Clearly, crystalline-assembling D–A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.

36 MATERIALS SCIENCE↗

DOE OSTI2025

A Theory of Ultrafast Charge Transfer Relaxation with Non-Innocent Solvent Molecules

In this work we revisit the photodynamics of tetracyanoethylene-hexamethylbenzene (TCNE- HMB), the molecular complex studied by Hochstrasser et al. [J. Chem. Phys. 100, 4797–4810, 1994] that has long challenged the applicability of Marcus’s theory of elec- tron transfer for predicting photochemical reactions. Using a novel black-box electronic structure algorithm (time-dependent density functional theory with one double, TD- DFT-1D) to efficiently run molecular dynamics that can treat charge recombination, we run ab initio surface hopping molecular dynamics and confirm that, for a polar solvent, charge recombination rates can be incredibly fast (indeed faster than the sol- vent relaxation time); for non-polar solvents, the rate is much slower. We demonstrate that, although Marcus theory cannot be directly applied, these nonequilibrium (and sometimes incredibly fast) photoexcited dynamics can be effectively explained within a two-state model without any evidence of a transition through a conical intersection. Most importantly, for this paradigmatic model system, we are able to identify two nuclear coordinates of interest (rather than the single coordinate predicted by Marcus or a full set of internal quantum modes studied by Bixon and Jortner): the solvent relaxation in the first shell (that strongly modulates the energies of the charge trans- fer state and differentiates time scales for relaxation) and a nuclear displacement in the TCNE-HMB complex arising from a handful of vibrations that induces non-Born Oppenheimer motion and eventually facilitates an abrupt electronic transition to the ground state. Altogether, these findings suggest a tractable generalization of Marcus theory for future simulations of photochemistry with non-innocent solvent environ- ments in the spirit of a Hamiltonian suggested by Stuchebrukhov (J. Chem. Phys. 107, 3821, 1997).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1990

Vibrational energy transfer in OH X 2Pi(i), v = 2 and 1

Using an IR-pump/UV-probe method in a flow discharge cell, vibrational energy transfer in OH X 2Pi(i) has been studied. OH is prepared in v = 2 by overtone excitation, and the time evolution of population in v = 2 and 1 monitored by laser-induced fluorescence. Rate constants for vibrational relaxation by the colliders H2O, NH3, CO2, and CH4 were measured. Ratios of rate constants for removal from the two states, k2/k1, range from two to five.

Raiche, George A.↗

NASA NTRS1992

Radiative interactions in nonequilibrium flows

The influence of vibrational and chemical nonequilibrium upon infrared radiative energy transfer in nonisothermal gases is investigated. Essential information is provided on rate equations, relaxation times, transfer equations, band absorption, and radiative flux equations. The methodology developed is applied to three specific cases. These are, absorbing-emitting species between isothermal parallel plates, radiating gases in the earth's atmosphere, and supersonic flow of premixed hydrogen and air in an expanding nozzle. The results obtained for different cases reveal that the extent of radiative interactions is reduced significantly under nonequilibrium conditions. The method developed can be easily extended to investigate radiative interactions in complex nonequilibrium flows.

Tiwari, S. N.↗

DOE OSTI2022

Interplay of structural fluctuations and charge carrier dynamics is key for high performance of hybrid lead halide perovskites

The ability of methylammonium lead triiodide (MAPbI 3 ) to achieve photoelectric conversion efficiency that is on par with crystalline silicon has led to a surge of interest in perovskite photovoltaics. However, an in-depth understanding of how the ubiquitous coupling between the fast rovibrational movements of the organic cations and the phonon vibrations of the inorganic framework affects the relaxation and recombination of hot carriers remains largely elusive. Access to such knowledge is critical to guide design and increase efficiency of new classes of perovskite solar cells. In this report, we report a time-domain ab initio investigation of temperature dependent excited state dynamics in MAPbI 3 , with particular emphasis on nuclear anharmonic effects. The observed strong anharmonicity is attributed to softness of the material and unusual dynamical coupling between the organic and inorganic components. At an elevated temperature, the hydrogen bonding between MA and iodines is weakened, enhancing rotation of MA cations, which become more dynamically disordered. As a result, thermal vibrations of the inorganic Pb–I sublattice are suppressed, and the lattice anharmonicity is decreased. Thermal fluctuations of the electronic energy levels are found to follow the trend of anharmonic motions of Pb and I atoms, with holes relaxing faster to the band edges than electrons, due to higher density of the hole states. While elevated temperature accelerates intraband carrier cooling, it slows nonradiative carrier recombination. The latter result is important for performance, since solar cells and other devices heat up during operation. The reported signatures of coupled structural dynamics of the organic cations and inorganic framework unravel the interplay between anomalous structural fluctuations and charge carrier dynamics, which is of particular importance for fundamental understanding of the structure–property relationships in hybrid metal halide perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1972

Post-threshold energy dependence of the cross section for endoergic processes - Vibrational excitation and reactive scattering.

The essential features of the translational energy dependence or excitation function for two types of endoergic collisional processes are deduced on the basis of information on the inverse, exoergic processes. Microreversibility is conveniently exploited via the symmetric field function, Y(E), which is uniquely determined at a given total energy, E. In the case of the vibrational excitation of diatomic molecules by atomic or molecular impact, use is made of the abundant data on the temperature dependence of the relaxation time.

Levine, R. D.↗

NASA NTRS1989

Vibrational relaxation of OH (X 2Pi sub i, v = 2)

A two-laser pump-and-probe technique is used to determine vibrational relaxation rates for the v = 2 level of the X 2Pi sub i state of the OH radical. In the present method, the time delay between the lasers is scanned at a given collider pressure, producing exponential decay whose rate as a function of collider pressure yields the rate constant. With the exception of ammonia, the values obtained are two to three orders of magnitude smaller than those found for relaxation of v = 1 in the A 2Sigma(+) excited state of OH.

Rensberger, Karen J.↗

DOE OSTI2022

Reversible motions and disordered structure of soft particles in amorphous solids

In amorphous solids, soft vibrational modes derived from normal mode analysis can be utilized to identify the soft particles that are prone to irreversible rearrangements. However, the normal mode analysis approach cannot explain why the spatial distributions of clustered soft particles do not change over time. We define a softness parameter based on the vibrational density of states calculated directly from molecular dynamics simulations with both the harmonic vibrations and anharmonic relaxations being properly captured at finite temperatures. This parameter spontaneously correlates with the real space atomic motions and the dynamics heterogeneity. Using the softness parameter, we show that the softest particles are confined within rigid cages. These particles keep rearranging reversibly without long-range diffusion. The moderately soft particles rearrange irreversibly, and the hard particles mainly participate in vibrations without rearrangement. Here, we also show that the soft particles form locally disordered structures, while the hard particles present strong ordering. These findings confirm the defective nature of soft particles, and provide insights on the nature of softness as the ability to rearrange, but not necessarily irreversibly.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Optical phonon dominated heat transport: A first-principles thermal conductivity study of BaSn 2

Acoustic phonons with long mean free paths have long been believed to control the lattice thermal conductivity κ L in solids dominantly. In this study, however, we demonstrate an optical phonon dominated κ L in BaSnS 2 . By solving the Peierls-Boltzmann transport equation, we predict a low diagonal lattice thermal conductivity κ L (D) of 0.34 W m -1 K -1 at 850 K, which is less than half the κ L (D) of SnS at the same temperature. Further calculations following the Allen-Feldman model suggest the additional off-diagonal lattice thermal conductivity κ L (OD) contributed by wavelike tunneling phonons. The κ L (OD) becomes pronounced at the high temperature ( 0.17 W m -1 K -1 at 850 K) and leads to a deviation of the temperature dependence of κ L from T -1 to T -0.76 , suggesting the potential lattice anharmonicity in BaSnS 2 . Further analyses indicate BaSnS 2 has over 68% of κ L contributed by optical phonons. We show this uncommon optical phonon dominated κ L is due to the relatively high group velocities of optical phonons in BaSnS 2 . The phonon mode visualization suggests these relatively high-velocity optical phonons correspond to the antiphase vibrations in BaSnS 2 monolayers, which is originated from the unique permutation of SnS 3 tetrahedra. Finally, by investigating the mode-resolved group velocity, relaxation time, and Grüneisen parameter, we attribute the intrinsic low κ L of BaSnS 2 to the soft lattice and the relatively high lattice anharmonicity induced by the Ba-S weak bonding and Sn(II) lone-pair electrons. Our study explicitly analyzes the microscopic mechanism of optical phonon dominated heat transport in BaSnS 2 and suggests it worthy of further experimental studies as an intrinsic low-κ L material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗