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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses

Here, the lattice vibrational dynamics in ultra-fragile Pt 57 Cu 23 P 20 and Pt 60 Cu 20 P 20 glasses were investigated using in situ inelastic neutron scattering to measure the evolution of the phonon density of states (DOS) through the glass transition, into the undercooled liquid phase, and through crystallization. The phonon DOS curves are remarkably similar for the undercooled liquids and the amorphous solids. The vibrational entropy was obtained with these phonon DOS curves, and changes in vibrational entropy caused by the glass transition are less than 0.05 k B /atom. For these highly fragile metal/metalloid glasses, the excess vibrational entropy of the undercooled liquid is about 0.5–1.5 Jmol -1 K -1 , compared to 0.1 Jmol -1 K -1 reported earlier for stronger Cu–Zr glasses. Our work suggests that, consistent with our previous report for less fragile metallic glasses, the fraction of the total excess entropy that is vibrational is small, and the discontinuity in excess entropy at the glass transition is mainly due to configurational entropy.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Delineating the Effects of Counterions on the Structural and Vibrational Properties of U(IV) Lindqvist Polyoxometalate Complexes

Herein we conducted a full investigation into the fundamental structural and vibrational properties of uranium(IV) Peacock−Weakley-type lacunary Lindqvist (W 10 ) polyoxometalate (POM) complexes. We recently demonstrated the importance of the secondary lattice elements in tuning the distortion of the D 4d symmetry in W 10 POM complexes, and here, we synthesized eight UW 10 complexes with different alkali metal counterions and evaluated how the composition and packing of counterion species affected complex structural and vibrational properties. Single-crystal X-ray diffraction analysis on complexes 1−8 revealed changes in structural distortion parameters as a function of differences in counterion configurations, while far-infrared and Raman spectra for 1−8 also demonstrated that vibrational mode frequencies were sensitive to changes in counterion composition and packing. To more effectively compare different counterion configurations, we developed counterion effective ionic radius (eIR) as a new structural parameter, and comparisons between structural distortion parameters and eIR values strongly suggested that modulation by the secondary lattice elements can affect structural and vibrational manifolds within POM complexes. Partial least squares (PLS) analysis was used to quantitatively evaluate correlations observed within this investigation, and PLS statistical models showed a strong correlation between counterion eIR and both structural distortion parameters and vibrational mode frequencies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photoinduced Dynamics with Constrained Vibrational Motion: FrozeNM Algorithm

Ab initio molecular dynamics (AIMD) simulation, analyzed in terms of vibrational normal modes, is a widely used technique that facilitates understanding of complex structural motions and coupling between electronic and nuclear degrees of freedom. Usually, only a subset of vibrations is directly involved in the process of interest. The impact of these vibrations can be evaluated by performing AIMD simulations by selectively freezing certain motions. In this paper, we present frozen normal mode (FrozeNM), a new algorithm to apply normal-mode constraints in AIMD simulations, as implemented in the nonadiabatic excited state molecular dynamics code. We further illustrate its capacity by analyzing the impact of normal-mode constraints on the photoinduced energy transfer between polyphenylene ethynylene dendrimer building blocks. Our results show that the electronic relaxation can be significantly slowed down by freezing a well-selected small subset of active normal modes characterized by their contributions in the direction of energy transfer. The application of these constraints reduces the nonadiabatic coupling between electronic excited states during the entire dynamical simulations. Furthermore, we validate reduced dimensionality models by freezing all the vibrations, except a few active modes. Altogether, we consider FrozeNM as a useful tool that can be broadly used to underpin the role of vibrational motion in a studied process and to formulate reduced models that describe essential physical phenomena.

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

Attosecond Probing of Coherent Vibrational Dynamics in CBr 4

A coherent vibrational wavepacket is launched and manipulated in the symmetric stretch (a1) mode of CBr 4 , by impulsive stimulated Raman scattering (ISRS) from nonresonant 400 nm laser pump pulses with various peak intensities on the order of tens of 10 12 W/cm 2 . Extreme ultraviolet (XUV) attosecond transient absorption spectroscopy (ATAS) records the wavepacket dynamics as temporal oscillations in XUV absorption energy at the bromine M 4,5 3d 3/2,5/2 edges around 70 eV. The results are augmented by nuclear timedependent Schrödinger equation simulations. Slopes of the (Br 3d 3/2,5/2 ) –1 10a 1 * core-excited state potential energy surface (PES) along the a 1 mode are calculated to be –9.4 eV/Å from restricted open-shell Kohn–Sham calculations. Using analytical relations derived for the small-displacement limit and the calculated slopes of the core-excited state PES, a deeper insight into the vibrational dynamics is obtained by retrieving the experimental excursion amplitude of the vibrational wavepacket and the amount of population transferred to the vibrational first-excited state as a function of pump-pulse peak intensity. Experimentally, the results show that XUV ATAS is capable of resolving oscillations in the XUV absorption energy on the order of a few to tens of meV with tens of femtosecond time precision. This corresponds to change in C–Br bond length on the order of 10 –4 to 10 –3 Å. The results and the analytic relationships offer a clear physical picture, on multiple levels of understanding, of how the pump-pulse peak intensity controls the vibrational dynamics launched by nonresonant ISRS in the small-displacement limit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Vibrational Properties of a Naturally Occurring Semiconducting van der Waals Heterostructure

We present vibrational properties of Franckeite, which is a naturally occurring van der Waals heterostructure consisting of two different semiconducting layers. Franckeite is a complex layered crystal composed of alternating SnS 2 -like pseudohexagonal and PbS-like pseudotetragonal layers stacked on top of each other, providing a unique platform to study vibrational properties and thermal transport across layers with mass density and phonon mismatches. Using micro-Raman spectroscopy and first-principles Raman simulations, we found that the PbS-like pseudotetragonal structure is mostly composed of Pb 3 SbS 4 . We also discovered several low-frequency Raman modes that originate from the intralayer vibrations of the pseudotetragonal layer. Using density functional theory, we determined all vibrational patterns of Franckeite, whose signatures are observed in the Raman spectrum. By studying temperature-dependent Raman spectroscopy (300–500 K), we have found different temperature coefficients for both pseudotetragonal and pseudohexagonal layers. Here, we believe that our study will help understand the vibration modes of its complex heterostructure and the thermal properties at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Optically Addressing Circularly Polarized Vibrations in Molecules

Circularly polarized (CP) vibrations are the nuclear-motion analog of CP light, emerging in molecules with non-Abelian point-group symmetry that support orthogonal and degenerate vibrational normal modes. Here, in this work, we theoretically explore the optical addressability of CP vibrations, motivated by their potential as nanoscale angular momentum states suitable for information storage and manipulation. We investigate how symmetry-breaking chemical modifications affect a molecule’s capacity to support CP vibrations. Notably, we find cases where modes retain their orthogonality and degeneracy in spite of such modifications, broadening the opportunities afforded by CP vibrations beyond non-Abelian point-group molecules. Prospects for experimental implementations using CP pump–probe techniques are briefly discussed.

group theory↗
DOE OSTI2025

The Effects of Shockwave Pressures on Ultrafast Vibrational Energy Transfer in BNFF, a Hydrogen-Free Energetic Material

Energy conversion in energetic materials from shock-wave-induced lattice compression to bond breaking critically depends on vibrational coupling and energy transfer between intra- and intermolecular vibrations, though the details of the mechanisms remain unknown. Herein, we indirectly tune the strength of intermolecular interactions in 3,4-bis(3-nitrofurazan-4-yl)furoxan (BNFF), a hydrogen-free energetic material characterized by van der Waals interactions, by applying high static pressure using a diamond anvil cell and monitoring vibrational energy transfer (VET) with ultrafast broadband infrared pump–probe spectroscopy. As BNFF is compressed from ambient pressure to 9 GPa, we find that VET accelerates by ∼ 0.9 ps/GPa. Density functional theory is applied in tandem with experiments to assign mode character and elucidate VET pathways. In conclusion, we find that furazan ring O–N–O vibrations, which are high-frequency detonation-relevant vibrational modes, experience increased sensitivity to lattice compression under shockwave pressures. These findings provide new mechanistic insight into how intermolecular interactions govern the rate and selectivity of VET.

Energy transfer↗
DOE OSTI2026

Vibrational Quantum-State-Controlled Reactivity in the O 2 + + C 3 H 4 Reaction

Quantum-state-controlled reactivity is a long-standing goal in the field of physical chemistry. In this work, we explore the vibrational-state-dependent behavior of the ion–molecule reaction between O 2 + in distinct vibrational states and two isomers of C 3 H 4 , allene (H 2 C 3 H 2 ) and propyne (H 3 C 3 H). While most products are formed regardless of the vibrational state of O 2 + , the branching ratios are influenced by vibrational excitation, and a new product, C 2 O + , appears exclusively in the excited-state reactions. This selective formation of C 2 O + demonstrates that vibrational excitation can effectively activate a reaction pathway, providing direct evidence of quantum-state control in the reactivity. These results represent an important step toward the goal of quantum-state-controlled chemistry in molecular systems.

Chemical reactions↗
DOE OSTI2023

Machine learning-based discovery of vibrationally stable materials

The identification of the ground state phases of a chemical space in the convex hull analysis is a key determinant of the synthesizability of materials. Online material databases have been instrumental in exploring one aspect of the synthesizability of many materials, namely thermodynamic stability. However, the vibrational stability, which is another aspect of synthesizability, of new materials is not known. Applying first principles approaches to calculate the vibrational spectra of materials in online material databases is computationally intractable. Here, a dataset of vibrational stability for ~3100 materials is used to train a machine learning classifier that can accurately distinguish between vibrationally stable and unstable materials. This classifier has the potential to be further developed as an essential filtering tool for online material databases that can inform the material science community of the vibrational stability or instability of the materials queried in convex hulls.

36 MATERIALS SCIENCE↗
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↗
DOE OSTI2022

Numerical study of pure rotational fs/ps CARS coherence beating at high pressure and for multi-species rotation-vibration non-equilibrium thermometry

Coherent anti-Stokes Raman scattering (CARS) has long been the gold standard for non-intrusively measuring gas temperature in reacting flows such as flames and plasmas. Recently, the development of ultrafast hybrid fs/ps CARS has enabled the exploitation of coherence beating between neighboring spectral lines to simultaneously measure rotational and vibrational temperatures from a single pure rotational spectrum. However, the influence of non-Boltzmann vibrational state distributions and limitations due to collisional dephasing at pressures greater than 1 atm remains unclear. In this work, we use spectral simulations to investigate the effects of non-Boltzmann vibrational state distributions and the applicability of coherence beating at pressures up to 10 atm. We show that short probe pulses can be leveraged to quantify non-Boltzmann vibrational state distributions of N2. Furthermore, we demonstrate that fs/ps CARS coherence beating can simultaneously provide sensitive measurements of rotational and vibrational temperatures of both O2 and N2 in air. A sensitivity analysis was conducted to qualitatively explain the accuracy and precision comparisons between probe delays.

Chen, Timothy Y. (ORCID:0000000330269767)↗
DOE OSTI2023

Activation of atomic transport via vibrational coupling-induced force fluctuations

Vibrational coupling, although well-explored in many fields, has seldom been investigated in the context of mass transport. In this Letter, we examine the impact of vibrational coupling on atomic transport using simple molecular dynamics simulations. Our study shows that the atomic transport can be activated when the natural frequency of the atomic slit is close to the natural frequency of the atom being transported. We uncover the presence of fluctuating forces induced by vibrational coupling with higher amplitudes observed when the coupling is strong. We show that the transport activation mechanism is due to the high force fluctuations that arise during strong vibrational coupling allowing the atom to temporarily surpass the transport barrier of the slit. Our findings will serve as a foundation for the continued examination of vibrational coupling in the realm of mass transport.

Physics↗
DOE OSTI2024

Influence of fourth-order vibrational corrections on semi-experimental (reSE) structures of linear molecules

Semi-experimental structures (reSE) are derived from experimental ground state rotational constants combined with theoretical vibrational corrections. They permit a meaningful comparison with equilibrium structures based on high-level ab initio calculations. Typically, the vibrational corrections are evaluated with second-order vibrational perturbation theory (VPT2). The amount of error introduced by this approximation is generally thought to be small; however, it has not been thoroughly quantified. Herein, we assess the accuracy of theoretical vibrational corrections by extending the treatment to fourth order (VPT4) for a series of small linear molecules. Typical corrections to bond distances are on the order of 10−5 Å. Larger corrections, nearly 0.0002 Å, are obtained to the bond lengths of NCCN and CNCN. A borderline case is CCCO, which will likely require variational computations for a satisfactory answer. Treatment of vibrational effects beyond VPT2 will thus be important when one wishes to know bond distances confidently to four decimal places (10−4 Å). Certain molecules with shallow bending potentials, e.g., HOC+, are not amenable to a VPT2 description and are not improved by VPT4.

Chemistry↗
DOE OSTI2021

Two-dimensional electronic–vibrational sum frequency spectroscopy for interactions of electronic and nuclear motions at interfaces

Significance Electronic–vibrational couplings are pivotal in many photo-induced processes at interfaces and surfaces. Two-dimensional electronic–vibrational sum frequency generation spectroscopy is a unique tool to decipher electronic–vibrational couplings for excited states of molecules at interfaces and surfaces, enabling the correlation of photo-induced electronic–vibrational manifolds with their subsequent time evolution of high-frequency vibrational modes. This technique is especially powerful to monitor ultrafast processes such as charge transfer, energy transfer, proton transfer, and proton-coupled charge transfer at interfaces and surfaces on a real-time basis.

Deng, Gang-Hua↗
DOE OSTI2023

Lattice vibrations and energy landscape of the isoelectronic semiconductor series CuBr, ZnSe, GaAs, and Ge: The special case of CuBr and its $\mathcal{d}$-level chemistry

Here we have examined the lattice vibrations and the energy landscape of the isoelectronic diamond and zincblende semiconductor series CuBr, ZnSe, GaAs, and Ge. Vibrations are found to be an increasing function of ionicity, with the cation sublattice always vibrating more strongly than the anion sublattice. These findings are consistent with density functional theory (DFT) calculations of the energy landscape and temperature-dependent molecular dynamics simulations of the atomic-position fluctuations. For CuBr, inclusion of the Cu 3d Hubbard U term is found necessary to stabilize the zincblende structure and to bring its vibrational amplitudes into agreement with experiment. In addition, vibrations are found to strongly affect the CuBr near-edge x-ray absorption fine structure that we have successfully modeled by including displacements in our theoretical Bethe-Salpeter equation calculations. Reverse Monte Carlo structural refinements using large atomic configurations to simultaneously fit x-ray absorption and x-ray total-scattering data support these conclusions, and they reveal strong Cu-Br first-neighbor correlations and asymmetric distributions of interatomic distances in the temperature ranges of both negative and positive thermal expansion. Delineation of the CuBr valence band photoelectron spectrum into its Cu 3d and Br 4p states uniquely reveals their covalent mixing and further supports the DFT results.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Bearing Fault Detection on Wind Turbine Gearbox Vibrations Using Generalized Likelihood Ratio-Based Indicators

Studies in condition monitoring literature often aim to detect rolling element bearing faults because they have one of the biggest shares among defects in turbo machinery. Accordingly, several prognosis and diagnosis methods have been devised to identify fault signatures from vibration signals. A recently proposed method to capture the rolling element bearing degradation provides the groundwork for new indicator families utilizing the generalized likelihood ratio test. This novel approach exploits the cyclostationarity and the impulsiveness of vibration signals independently in order to estimate the most suitable indicators for a given fault. However, the method has yet to be tested on complex experimental vibration signals such as those of a wind turbine gearbox. In this study, the approach is applied to the National Renewable Energy Laboratory Wind Turbine Gearbox Condition Monitoring Round Robin Study data set for bearing fault detection purposes. The data set is measured on an experimental test rig of a wind turbine gearbox; hence the complexity of the vibration signals is similar to a real case. The outcome demonstrates that the proposed method is capable of distinguishing between healthy and damaged vibration signals measured on a complex wind turbine gearbox.

condition monitoring↗
DOE OSTI2020

Vibrational Spectroscopic Monitoring of the Gelation Transition in Nafion Ionomer Dispersions

Infrared and Raman spectroscopy techniques were applied to investigate the drying and aggregation behavior of Nafion ionomer particles dispersed in aqueous solution. Gravimetric measurements aided the identification of gel-phase development within a series of time-resolved spectra that tracked transformations of a dispersion sample during solvent evaporation. A spectral band characteristic of ionomer sidechain end group vibration provided a quantitative probe of the dispersion-to-gel change. For sets of attenuated total reflection Fourier transform infrared (ATR FT-IR) spectra, adherence to Beer's law was attributed to the relatively constant refractive index in the frequency region of hydrated –SO$^{–}_{3}$ group vibrations as fluorocarbon-rich ionomer regions aggregate in forming the structural framework of membranes and thin films. Although vibrational bands associated with ionomer backbone CF 2 stretching vibrations were affected by distortion characteristic of wavelength-dependent refractive index change within a sample, the onset of band distortion signaled gel formation and coincided with ionomer mass % values just below the critical gelation point for Nafion aqueous dispersions. Similar temporal behavior was observed in confocal Raman microscopy experiments that monitored the formation of a thin ionomer film from an individual dispersion droplet. For the ATR FT-IR spectroscopy and confocal Raman microscopy techniques, intensity in the water H–O–H bending vibrational band dropped sharply at the ionomer critical gelation point and displayed a time dependence consistent with changes in water content derived from gravimetric measurements. The reported studies lay groundwork for examining the impact of dispersing solvents and above-ambient temperatures on fluorinated ionomer transformations that influence structural properties of dispersion-cast membranes and thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2020

1-D imaging of rotation-vibration non-equilibrium from pure rotational ultrafast coherent anti-Stokes Raman scattering

We present one-dimensional (1-D) imaging of rotation-vibration non-equilibrium measured by two-beam pure rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS). Simultaneous measurements of the spatial distribution of molecular rotation-vibration non-equilibrium are critical for understanding molecular energy transfer in low temperature plasmas and hypersonic flows. However, non-equilibrium CARS thermometry until now was limited to point measurements. The red shift of rotational energy levels by vibrational excitation was used to determine the rotational and vibrational temperatures from 1-D images of the pure rotational spectrum. Vibrational temperatures up to 5500 K were detected in a CH4/N2 nanosecond-pulsed pin-to-pin plasma within 2 mm near the cathode. As a result, this approach enables study of non-equilibrium systems with 40 µm spatial resolution.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗