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At least 37 records · Page 2

First-principles electron-phonon interactions and polarons in the parent cuprate La 2 CuO 4

Understanding electronic interactions in high-temperature superconductors is an outstanding challenge. In the widely studied cuprate materials, experimental evidence points to strong electron-phonon ( e -ph) coupling and broad photoemission spectra. Yet, the microscopic origin of this behavior is not fully understood. Here, we study e -ph interactions and polarons in a prototypical parent (undoped) cuprate, La 2 CuO 4 (LCO), by means of first-principles calculations. Leveraging parameter-free Hubbard-corrected density functional theory, we obtain a ground state with the band gap and Cu magnetic moment in nearly exact agreement with experiments. This enables a quantitative characterization of e -ph interactions. Our calculations reveal two classes of longitudinal optical (LO) phonons with strong e -ph coupling to hole states. These modes consist of bond stretching and bond bending in the Cu-O plane as well as vibrations of apical O atoms. The hole spectral functions, obtained with a cumulant method that can capture strong e -ph coupling, exhibit broad quasiparticle peaks with a small spectral weight ( Z ≈ 0.25 ) and pronounced LO-phonon sidebands characteristic of polaron effects. Our calculations predict features observed in photoemission spectra, including a 40-meV peak in the e -ph coupling distribution function not explained by existing models. These results show that the universal strong e -ph coupling found experimentally in doped lanthanum cuprates is also present in the parent compound, and elucidate its microscopic origin. Published by the American Physical Society 2025

Chang, Benjamin K. (ORCID:0000000313049324)↗

High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region

First high-resolution spectra of cold (~35 K) singlet bromomethylene HCBr in the CH stretching (v 1 ) region from 2770 to 2850 cm-1 are reported using near quantum shot-noise limited laser absorption methods in a slit jet supersonic discharge expansion source. Three rovibrational bands are identified at high S/N (20:1 - 40:1) and rotationally assigned to i) the CH stretch fundamental (v 1 ) band $\tilde{X}$(1,0,0) ← $\tilde{X}$ (0,0,0) and ii) vibrational hot bands ($\tilde{X}$(1,1,0) ← $\tilde{X}$(0,1,0) and $\tilde{X}$(1,0,1) ← $\tilde{X}$(0,0,1)) arising from vibrationally excited HCBr populated in the discharge with single quanta in either the H–C–Br bend (v 2 ) or C–Br stretch (v 3 ) modes. Precision rotational constants are reported for a total of six states, with an experimentally determined CH stretch vibrational frequency (2799.38 cm -1 ) in good agreement with previous low-resolution fluorescence studies. Detailed analysis of the fundamental v 1 band highlights the presence of perturbations in the $\tilde{X}$(1,0,0) level, which we tentatively attribute to arise from the nearby triplet state $\tilde{a}$(0,0,1) through spin-orbit interaction or the multiple quanta $\tilde{X}$(0,2,1) singlet state via c-type Coriolis coupling. Reduced-Doppler resolution (60 MHz) in the slit-jet IR spectrometer permits clear observation of nuclear spin hyperfine structure, with experimental line shapes well reproduced by nuclear quadrupole/spin-rotation coupling constants from microwave studies. Lastly, the a-type to b-type transition intensity ratio for the fundamental CH stretch band is notably larger than predicted by a bond-dipole model, which from high level ab initio quantum calculations (CCSD(T)/PVQZ) can be attributed to vibrationally induced “charge-sloshing” of electron density along the polar C–Br bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared spectroscopy of RG–Co + (H 2 O) complexes (RG = Ar, Ne, He): The role of rare gas “tag” atoms

RG n –Co + (H 2 O) cation complexes (RG = Ar, Ne, He) are generated in a supersonic expansion by pulsed laser vaporization. Here, complexes are mass-selected using a time-of-flight spectrometer and studied with infrared laser photodissociation spectroscopy, measuring the respective mass channels corresponding to the elimination of the rare gas “tag” atom. Spectral patterns and theory indicate that the structures of the ions with a single rare gas atom have this bound to the cobalt cation opposite the water moiety in a near-C 2v arrangement. The O–H stretch vibrations of the complex are shifted compared to those of water because of the metal cation charge-transfer interaction; these frequencies also vary systematically with the rare gas atom attached. The efficiencies of photodissociation also vary with the rare gas atoms because of their widely different binding energies to the cobalt cation. The spectrum of the argon complex could only be measured when at least three argon atoms were attached. In the case of the helium complex, the low binding energy allows the spectra to be measured for the low-frequency H–O–H scissors bending mode and for the O–D stretches of the deuterated analog. The partially resolved rotational structure for the antisymmetric O–H and O–D stretches reveals the temperature of these complexes (6 K) and establishes the electronic ground state. The helium complex has the same 3 B 1 ground state as the tag-free complex studied previously by Metz and co-workers (2013), but the A rotational constant is contaminated by vibrational averaging from the bending motion of the helium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas-phase preparation of the dibenzo[ e,l ]pyrene (C 24 H 14 ) butterfly molecule via a phenyl radical-mediated ring annulation

A high temperature phenyl-mediated addition–cyclization–dehydrogenation mechanism to form peri-fused polycyclic aromatic hydrocarbon (PAH) derivatives—illustrated through the formation of dibenzo[e,l]pyrene (C 24 H 14 )—is explored through a gas-phase reaction of the phenyl radical (C 6 H 5 ˙) with triphenylene (C 18 H 12 ) utilizing photoelectron photoion coincidence spectroscopy (PEPICO) combined with electronic structure calculations. Low-lying vibrational modes of dibenzo[e,l]pyrene exhibit out-of-plane bending and are easily populated in high temperature environments such as combustion flames and circumstellar envelopes of carbon stars, thus stressing dibenzo[e,l]pyrene as a strong target for far-IR astronomical surveys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational spectroscopy analysis of silica and silicate glass networks

Vibrational spectroscopy has been widely used to investigate various structural aspects of the glass network, and there are a plethora of papers reporting subtle but consistent changes in infrared and Raman spectral features of glass upon alterations of glass compositions, thermal histories, mechanical stresses, or surface treatments. However, interpretations of such spectral features are still obscured due to the lack of well-established physical principles accurately describing vibrational modes of the non-crystalline glass network. Due to the non-equilibrium nature of the glass network, three-dimensionally connected without any long-range orders, vibrational spectral features of glass cannot be interpreted using the analogy with those of isolated molecular moieties or crystalline counterparts. Here, this feature article explains why such comparisons are outdated and describes the recent advances made from theoretical calculations of vibrational spectral features of amorphous networks or comparisons of computational results with experimental data. For the interpretation of vibrational spectral features of silica and silicate glasses, the following empirical relationships are suggested: (i) the intensity-weighted peak position of the Si-O-Si stretch mode negatively correlates with the weighted average of the Si-O bond length distribution, and (ii) the broad band of the Si-O-Si bending mode negatively correlates with the Si-O-Si bond angle distribution. Selected examples of vibrational spectroscopic imaging of surface defects are discussed to deliberate the implication of these findings in the structure-property relationship of silica and silicate glass materials. Unanswered questions and continuing research challenges are identified.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states

We report a photodetachment spectroscopy and high-resolution resonant photoelectron imaging study of cryogenically-cooled 2-naphthoxide anions (C 10 H 7 O - ). The photodetachment spectrum revealed a dipole-bound state (DBS) 202(4) cm -1 below the detachment threshold and thirty-eight resonances corresponding to the vibrational levels of the DBS. By tuning the detachment laser to these above-threshold resonances, we obtained thirty-eight resonantly-enhanced photoelectron spectra, which were highly non-Franck-Condon as a result of mode-selective vibrational auto-detachment from the DBS. The resonances were assigned by comparing the resonant and non-resonant photoelectron spectra, assisted by the computed vibrational frequencies. Specifically, vibrational features with low Franck-Condon factors or from Franck-Condon-forbidden vibrational modes were significantly enhanced in the resonant photoelectron spectra, resulting in much richer spectroscopic information. The electron affinity of the 2-naphthoxy radical was measured accurately to be 19,387(4) cm -1 or 2.4037(5) eV. In addition, a total of seventeen vibrational frequencies were obtained for the 2-naphthoxy radical. In particular, seven Franck-Condon-forbidden out-of-plane bending modes, including the two lowest frequency modes (ν 48 at 102 cm -1 and ν47 at 171 cm -1 ), were observed, demonstrating the advantages of combining photodetachment spectroscopy and resonant photoelectron spectroscopy in obtaining vibrational information for polar radical species via DBS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards complete assignment of the infrared spectrum of the protonated water cluster H + (H 2 O) 21

The spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H + (H 2 O) n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H + (H 2 O) 21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Drop impact tester development for spent nuclear fuel vibration integrity study

The accumulated damage of SNF rod is defined as the integrated damage induced by the SNF assembly harmonic vibrations and SNF assembly & cask system contact interactions induced transient shocks, experienced by SNF rods during normal conditions of transportation (NCT). The CIRFT technology has provided means to resolve/understand the SNF rod harmonic vibration reliability issues associated with maximum axial clad tubing stress induced by SNF inertia related dynamic bending loading. However, the SNF rod integrity in association with the transient shock loads during NCT through dynamic contact interactions among SNF assembly cannot be investigated systematically through CIRFT technology alone. Thus, the proposed drop impact tester development become a viable tool for SNF system transient shock effect investigation. Furthermore, the transient shocks induced loading mode is normally perpendicular to the SNF rod axial orientation, i.e., in a transverse orientation to the SNF rod. To proceed with such loading mode investigation, a new device, “SNF Drop Impact Tester” that provides the transverse impact shock load onto a SNF rod through a free-drop projectile was developed in FY20 for SNF System Vibration Reliability Investigation; where the SNF system contact impact intensity can be calibrated accordingly with projectile weight and projectile head geometry. This newly developed research tool can further provide a detailed understanding about the effect of dynamic contact-interaction loadings; and combined harmonic vibration and transient shock loading modes on the fatigue damage evolution of the HBU SNF under NCT.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Vibrational spectroscopy of uranium tetrafluoride hydrates

Uranium tetrafluoride (UF 4 ) is an important intermediate in the production of UF6 and nuclear fuel. Historical characterization of UF 4 with Raman spectroscopy was plagued with ambiguity until the first accurate Raman spectrum was published by our group in 2016. Although generally considered to be relatively stable, UF 4 can hydrolyze to form numerous UF 4 hydrates that may play a role in future uranium waste forms. In contrast to anhydrous UF 4 , the hydrates, with their OH stretch and HOH bending modes, can be spectroscopically characterized by the type and degree of water bonding in the crystal lattice, which can yield additional information about their crystal structure. Herein, vibrational spectroscopy (Raman and infrared) was used to characterize three different UF 4 hydrates: UF 4 (H 2 O) 0.33 , U 3 F 12 (H 2 O), and UF 4 (H 2 O) 2.5 . Spectra show the different hydrates vary in the number of observed bands, full-width half-maximum of the bands, and band intensity. These differences are due to varying interactions between the OH stretch and HOH bending modes with UF 4 and the polymeric UF 4 structure in the crystal lattice. These vibrational data, in combination with spectral fitting and crystallographic structures measured with powder X-ray diffraction and single crystal X-ray diffraction, provide unique details on the location of water molecules in the crystal lattice of hydrated UF 4 , and provide an interesting contrast to the vibrational spectra of anhydrous UF 4 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Probing the Dipole-Bound State in the 9-Phenanthrolate Anion by Photodetachment Spectroscopy, Resonant Two-Photon Photoelectron Imaging, and Resonant Photoelectron Spectroscopy

Valence-bound anions with a dipolar core can support dipole-bound states (DBSs) below the electron detachment threshold. The highly diffuse DBS observed is usually of σ symmetry with an s-like orbital. Recently, a π-type DBS was observed experimentally in the 9-anthrolate anion (9AT – ) and it was shown to be stabilized due to the large anisotropic polarizability of the 9AT core. To confirm the general existence of π-DBS and its structural dependence, here we report an investigation of the 9-phenanthrolate anion (9PT – ), which has a different structure and lower symmetry than 9AT – . Photodetachment spectroscopy revealed a DBS 257 cm -1 below the detachment threshold of 9PT – at 19,627 cm -1 (2.4334 eV). Resonant two-photon photoelectron imaging indeed showed a π symmetry for the DBS. Similar to that observed in 9AT – , the π-DBS in 9PT – is also stabilized by the anisotropic polarizability of the 9PT core and accessed via non-adiabatic population transfer from the initially populated σ-DBS. Photodetachment spectroscopy unveiled nine above-threshold vibrational resonances of the DBS, resulting in nine highly non-Franck-Condon resonant photoelectron spectra by tuning the detachment laser to the vibrational resonances. In conclusion, the combination of photodetachment spectroscopy and resonant photoelectron spectroscopy allowed frequencies for nine vibrational modes of the 9-phenathroxy radical to be measured, including the six lowest frequency bending modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flexocaloric effect in superelastic materials

We present a combined theoretical–experimental study of flexocaloric effects in superelastic materials exhibiting structural transitions. We study a Ginzburg–Landau model combined with a vibrational model for a beam near a ferroelastic transition loaded with a three-point bending setup. We also perform experiments on a Cu–Al–Ni single crystal undergoing a martensitic transition. We measure bent beam profiles, vertical force vs vertical deflection during a slow isothermal process, time evolution of the bending and unbending amplitudes, and the evolution of temperature profiles. We also compute the evolution of heat source and heat sink profiles. Finally, we study the location of acoustic emission events during the bending/unbending experiment. Our observations are consistent with the model predictions and allow us to identify the main physical parameters relevant for flexocaloric applications.

36 MATERIALS SCIENCE↗

Optimizing Deep Geothermal Drilling for Energy Sustainability in the Appalachian Basin

This study investigates the geological and geomechanical characteristics of the MIP 1S geothermal well in the Appalachian Basin to optimize drilling and address the wellbore stability issues encountered. Data from well logs, sidewall core analysis, and injection tests were used to derive elastic and rock strength properties, as well as stress and pore pressure profiles. A robust 1D-geomechanical model was developed and validated, correlating strongly with wellbore instability observations. This revealed significant wellbore breakout, widening the diameter from 12 ¼ inches to over 16 inches. Advanced technologies like Cerebro Force™ In-Bit Sensing were used to monitor drilling performance with high accuracy. This technology tracks critical metrics such as bit acceleration, vibration in the x, y, and z directions, Gyro RPM, stick-slip indicators, and bending on the bit. Cerebro Force™ readings identified hole drag caused by poor hole conditions, including friction between the drill string and wellbore walls and the presence of cuttings or debris. This led to higher torque and weight on bit (WOB) readings at the surface compared to downhole measurements, affecting drilling efficiency and wellbore stability. Optimal drilling parameters for future deep geothermal wells were determined based on these findings.

Environmental Sciences & Ecology↗

Inelastic Neutron Spectra of Uranium Tetrafluoride Hydrate, UF 4 (H 2 O) 2.5

Uranium tetrafluoride hydrate (UFH) is formed by immersing anhydrous UF4 under water for 12 h. UFH is therefore clearly a chemical species of environmental concern, as anhydrous UF4 is an intermediate uranium form in the nuclear fuel cycle. We use inelastic neutron scattering (INS) to probe the full vibrational spectra of UFH and its deuterated analogue in an effort to improve the fundamental understanding of its vibrational spectra. Coupled with density functional theory (DFT) calculations, the first for this compound, and full spectral modeling, we generate the complete vibrational spectra of UFH and compare them to prior optical spectroscopic results. In particular, the combination of DFT with INS allows us to identify multiple distinct chemical environments in the water bending and OH stretching regions. Whereas the water molecules directly bound to the U atoms execute OH stretching around 3600 cm –1 , a second class of H-bonded waters vibrate below 3000 cm –1 , an indicator of strong H bonding. In addition, a class of librational water modes are observed between 400 and 900 cm–1, which themselves can be separated in energy according to their chemical environments. Furthermore, measurements presented herein directly assist in the assignment of certain spectral features in the infrared spectrum and will inform future investigations of UFH for environmental or forensics purposes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Behavior of Long-Chain Hydrocarbons at High Pressures and Temperatures

Although long-chain aliphatic hydrocarbons are documented in meteorites, their origin is poorly understood. A key question is whether they are pristine or a byproduct of terrestrial alteration? Thus, to understand if these long-chain hydrocarbons are indigenous, it will be important to explore their thermodynamic and mechanical stability at conditions experienced by extraterrestrial objects during atmospheric entry and passage. Extreme pressures and temperatures experienced by meteorites are likely to alter the molecular organization of these long-chain hydrocarbons. These structural changes associated with extreme conditions are often documented via laboratory-based Raman spectroscopic measurements. So far, Raman spectroscopic measurements have investigated the effect of static compression on the aliphatic hydrocarbons. The effect of temperature on the structural changes remains poorly explored. To bridge this gap, in this study, we have explored the behavior of two aliphatic hydrocarbons at simultaneously high pressures and temperatures. We have used a resistively heated diamond anvil cell. On compression to moderate pressures, the appearance of new vibrational modes in the low-energy region confirms prior studies and is related to the bending of the linear chains. Upon heating to ~220 °C, we note that the new low-energy mode undergoes softening. The mode softening is likely due to the combination of unbending of the alkane chain and mode anharmonicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transient vibration and product formation of photoexcited CS 2 measured by time-resolved x-ray scattering

Here, we have observed details of the internal motion and dissociation channels in photoexcited carbon disulfide (CS 2 ) using time-resolved x-ray scattering (TRXS). Photoexcitation of gas-phase CS 2 with a 200 nm laser pulse launches oscillatory bending and stretching motion, leading to dissociation of atomic sulfur in under a picosecond. During the first 300 fs following excitation, we observe significant changes in the vibrational frequency as well as some dissociation of the C–S bond, leading to atomic sulfur in the both 1 D and 3 P states. Beyond 1400 fs, the dissociation is consistent with primarily 3 P atomic sulfur dissociation. This channel-resolved measurement of the dissociation time is based on our analysis of the time-windowed dissociation radial velocity distribution, which is measured using the temporal Fourier transform of the TRXS data aided by a Hough transform that extracts the slopes of linear features in an image. The relative strength of the two dissociation channels reflects both their branching ratio and differences in the spread of their dissociation times. Measuring the time-resolved dissociation radial velocity distribution aids the resolution of discrepancies between models for dissociation proposed by prior photoelectron spectroscopy work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of interfacial vibrational coupling on surface wettability and water transport

Here, we report that the atomic-scale vibrational coupling at the solid-fluid interface can substantially alter the interfacial properties such as wettability and fluid slip. The wettability of water droplets on substrates subjected to various vibrational frequencies is studied using molecular dynamics simulation. The contact angle increases (i.e., becomes more hydrophobic) when the oscillation frequency of the substrate matches the intermolecular bending frequency of liquid water. We investigate the underlying mechanism by examining the dynamics of water molecules at the interface and find that the temporal contact between the solid and fluid is shorter when the frequencies match, resulting in weak solid-fluid adsorption. We further report that the vibrational match at the interface reduces wall-fluid friction and enhances water transport through the nanopore. Our findings demonstrate the importance of the atomic-scale vibrational coupling at the solid-fluid interface on the physicochemical behavior of nanodevices and biological nanochannels.

74 ATOMIC AND MOLECULAR PHYSICS↗

On the in-plane vibrations and electromechanical resonance characteristics of non-uniformly polarized rectangular piezoelectric wafers: Selective mode-type excitation and specific mode enhancement

Here, we investigate the in-plane vibrations and electromechanical resonance characteristics of non-uniformly polarized rectangular piezoelectric wafers. Non-uniform polarization is represented as a non-uniform electromechanical coupling coefficient using a polarization function. Governing equations are derived for the forced in-plane vibrations of a thin wafer under the assumption of generalized plane stress. The effect of non-uniform polarization is explicitly obtained in the forcing terms of the governing equations. These equations are then recast into a variational weak form that is then solved using the finite element method to obtain the displacement fields for different modes. The electromechanical response of a non-uniformly polarized piezoelectric wafer is derived in terms of the out-of-plane displacement profile on the surface of the wafer. Using the derived analytical expression, a necessary and sufficient condition for the presence/absence of a vibrational mode in the electromechanical impedance spectrum is obtained. Based on this condition, criteria for selective mode-type excitation and specific mode enhancement of vibrational modes in the electromechanical impedance spectrum are postulated. Selective mode-type excitation of in-plane extensional and shear modes is demonstrated for a square wafer and that of in-plane bending modes is demonstrated for a rectangular wafer. Specific mode enhancement is demonstrated for both square and rectangular wafers. In addition, it is also demonstrated how the criteria can be used to suppress specific vibrational modes in the electromechanical impedance spectrum. The proposed methodology of using non-uniformly polarized piezoelectric wafers finds application in the design of single element transducers with multi-frequency operation, frequency-tuned receivers/sensors, acoustic holograms, designing acoustic beams of prescribed shape/lobes, and other non-traditional applications such as information storage.

36 MATERIALS SCIENCE↗

Rotational Modulation of à 2 A State Photodissociation of HCO via Renner-Teller Nonadiabatic Transitions

By examining the product-state distribution of a prototypical non- adiabatic predissociation system, HCO($Ã^2A''–\tilde X^2A'$), we demonstrate here that the dissociation dynamics is strongly modulated by parent rotational quantum numbers. The predissociation of the nominal ($ν_{\text{C–H}} = 0, ν_{\text{bend}}, ν_{\text{C–O}} = 1$) vibronic levels of the $AÃ^2A''$ state surprisingly gives rise to both vibrational ground and excited states of the CO product, despite the assumed spectator nature of the CO moiety. This anomaly is attributed to the dependence of the lifetime of the vibronic resonance facilitated by the Renner–Teller interaction on the parent rotational angular momentum quantum numbers coupled with transient intensity borrowing from nearby vibronic resonances with $ν_{\text{C–O}} = 0$. This unique phenomenon is a purely quantum mechanical behavior that has no classical analogue.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗