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DOE OSTI2024

Vibrational study of CO, O 2 , and H 2 Adsorbed on the CoCrFeNi (110) High Entropy Alloy Surface

The vibrational properties of CO, O 2 , and H 2 molecularly or dissociatively adsorbed on a CoCrFeNi(110) surface have been probed using highresolution energy loss spectroscopy (HREELS) and modeled using density functional theory (DFT) calculations. Large (~20 mm3) single-crystal, quaternary face-centered cubic CoCrFeNi was synthesized via a modified Czochralski technique. We show strong evidence that CO adsorbs primarily on bridge and on-top sites in compositionally varied local environments, which reflect the random, multielemental surface composition inherent in a high entropy alloy. A variation of adsorption sites is also found with oxygen, which exhibits two broad groups of modes. Comparison to previous photoemission and theoretical studies suggests that the higher energy modes consist primarily of local CrO x species, while the lower energy modes are due to oxygen atoms adsorbed on other metal sites. Unlike CO and O 2 , HREELS upon H 2 adsorption shows only two much narrower modes and is consistent with atomic adsorption on 3-fold hollow sites. The hypothesized adsorption sites for all three species are directly corroborated by our DFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Cosolvent-tuned interactions in ionic liquids: A vibrational and quantum-chemical study of ethylene glycol ratio effects

Ionic liquids (ILs) are attractive media for CO 2 capture but remain limited by viscosity and cost. Blending ILs with ethylene glycol (EG) is a practical route to mitigate these constraints, yet the molecular origins of cosolvent effects and their dependence on composition are not well resolved. We combine Fourier-transform infrared (FT-IR) spectroscopy with quantum-chemical (DFT) analysis to elucidate how the IL:EG molar ratio modulates intermolecular interactions and electronic structure. Computed vibrational frequencies enable mode assignment and deconvolution of overlapping bands, revealing systematic, ratio-dependent shifts and broadenings in (i) EG O–H stretching, (ii) cation and EG C–H stretchings (imidazolium C2–H, C4–H, C5–H, methyl and ethyl groups, -CH2 of EG), (iii) anion signature modes (e.g., CN motifs), and (iv) EG C–O and C–C stretchings, consistent with the redistribution of hydrogen-bonding networks. Molecular electrostatic potential (MESP) maps quantify attenuation of extreme potential regions with increasing EG, indicating progressive screening of cation–anion electrostatic interactions. Quantum Theory of Atoms in Molecules (QTAIM) identifies emergent bond critical points between EG and the IL ions, while Reduced Density Gradient–Noncovalent Interaction (RDG–NCI) analysis differentiates strong directional hydrogen bonds from dispersive contacts across compositions. Together, these results show that EG fraction controls a switch from predominantly ion–ion to mixed ion–EG coordination, altering local polarity and polarizability that underlie the observed FT-IR trends. The framework provides composition–structure–spectrum relationships that can guide rational selection of IL:EG ratios to balance favorable molecular interactions with practical performance targets in scalable CO 2 capture systems.

DAC↗

DOE OSTI2020

Machine learning bridges local static structure with multiple properties in metallic glasses

A long-standing challenge in the metallic glass (MG) community has been how to quantitatively gauge the influence of the intricate local packing environment on the response (such as the propensity for atomic rearrangement) of the atomic configuration to external stimuli. Here we establish this structure–property relation by representing the complex amorphous structure using a single, flexibility-orientated structural quantity. This structural flexibility (SF) couples to a bona fide structural representation, the pair distribution function (PDF) of individual atoms, through a weighting function that reflects what matters in the static atomic configuration to dynamic responses. Machine learning is used, employing microscopic flexibility volume as the supervisory signal, to establish via direct regression an optimized weighting vector, which is proven robust for all quenching rates, deformation conditions, and different compositions in a given (e.g., Cu x Zr 100-x ) alloy system. Additionally, the SF is evaluated solely from the particle positions (PDF), for any structure variation, from the atomic scale up to sample average. Strong correlations are demonstrated between SF and a broad range of properties, including vibrational, diffusional, as well as elastic and plastic relaxation responses.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Magnetic and Optical Properties of Au–Co Solid Solution and Phase-Separated Thin Films and Nanoparticles

The chemical composition and morphology of Au x Co 1–x thin films and nanoparticles are controlled via a combination of cosputtering, pulsed laser-induced dewetting (PLiD), and annealing, leading to tunable magnetic and optical properties. Regardless of chemical composition, the as-deposited thin films and as-PLiD nanoparticles are found to possess a face-centered cubic (FCC) Au x Co 1–x solid-solution crystal structure. Annealing results in large phase-separated grains of Au and Co in both the thin films and nanostructures for all chemical compositions. The magnetic and optical properties are characterized via vibrating sample magnetometry (VSM), ellipsometry, optical transmission spectroscopy, and electron energy loss spectroscopy (EELS). Despite the exceptionally high magnetic anisotropy inherent to Co, the presence of sufficient Au (72 atom %) in the Au x Co 1–x solid solution results in superparamagnetic thin films. Among the as-PLiD nanoparticle samples, an increased Co composition leads to a departure from traditional ferromagnetism in favor of wasp-waisted hysteresis caused by magnetic vortices. Phase separation resulting from annealing leads to ferromagnetism for all compositions in both the thin films and nanoparticles. The optical properties of Au x Co 1–x nanostructures are also largely influenced by the chemical morphology, where the Au x Co 1–x intermixed solid solution has significantly damped plasmonic performance relative to pure Au and comparable to pure Co. Phase separation greatly enhances the quality factor, optical absorption, and electron energy loss spectroscopy (EELS) signatures. The enhancement of the localized surface plasmon resonances (LSPRs) scales with the reduction in Co composition, despite EELS evidence that excitation of the Co portions of a nanoparticle can provide a similar, and in some instances enhanced, LSPR resonance compared to Au. This behavior, however, is seemingly limited to the LSPR dipole mode, while higher-order modes are greatly damped by a Co aloof position. As a result, this observed magneto-plasmonic functionality and tunability could be applicable in biomedicine, namely, cancer therapeutics.

annealing (metallurgy)↗

DOE OSTI2023

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

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

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2026

The Interplay of Pauli Repulsion, Electrostatics, and Field Inhomogeneity for Blueshifting and Redshifting Vibrational Probe Molecules

Many molecules' vibrational frequencies are sensitive to intermolecular electric fields, enabling them to probe the field in complex molecular environments. However, it is often unclear whether the probe is responding to the local electric field or other types of intermolecular interactions, inhibiting interpretation of the frequency and effectiveness as probes. This is especially true for molecules whose vibrational frequencies blueshift instead of the more typical redshift in hydrogen bonding configurations. In this work, we computationally investigate the causes of redshifting versus blueshifting over a range of vibrational reporters. First, we apply adiabatic energy decomposition analysis to a paradigmatic set of probes, finding that redshifting only occurs when electrostatic interactions are strong enough to overcome the dominant and large blueshifting contribution of Pauli repulsion. Furthermore, we demonstrate that field inhomogeneity can further shift the frequency of many probes substantially to either reinforce or counteract the shift expected from a homogeneous field. We find that redshifting is reinforced by electric field inhomogeneity, otherwise field inhomogeneity further weakens the electrostatic contribution relative to Pauli repulsion, leading to blueshifting. Further calculations indicate that the probe's response to field inhomogeneity can be understood by considering the mass of the atoms involved in the stretching mode and sign of the electric field. In explaining the interplay of different intermolecular interactions and field inhomogeneity for many probes, our results should enable the use and interpretation of spectroscopic probes and their connection to electric fields in more complex systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Phonon-Induced Localization of Excitons in Molecular Crystals from First Principles

The spatial extent of excitons in molecular systems underpins their photophysics and utility for optoelectronic applications. Phonons are reported to lead to both exciton localization and delocalization. However, a microscopic understanding of phonon-induced (de)localization is lacking, in particular, how localized states form, the role of specific vibrations, and the relative importance of quantum and thermal nuclear fluctuations. Here, we present a first-principles study of these phenomena in solid pentacene, a prototypical molecular crystal, capturing the formation of bound excitons, exciton-phonon coupling to all orders, and phonon anharmonicity, using density functional theory, the ab initio GW-Bethe-Salpeter equation approach, finite-difference, and path integral techniques. In this study, we find that for pentacene zero-point nuclear motion causes uniformly strong localization, with thermal motion providing additional localization only for Wannier-Mott-like excitons. Anharmonic effects drive temperature-dependent localization, and, while such effects prevent the emergence of highly delocalized excitons, we explore the conditions under which these might be realized

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2026

From bulk to surface: Structure and dynamics of amorphous alumina from deep potential molecular dynamics

Understanding the atomic-scale structure and dynamics of amorphous oxide surfaces is essential for interpreting their chemical reactivity, mechanical stability, and interfacial behavior, yet direct experimental characterization remains challenging. We employ Deep Potential (DP) molecular dynamics to generate large-scale, ab initio -quality models of amorphous Al 2 O 3 bulk glasses and melt-quenched free surfaces, enabling a quantitative analysis of both structure and relaxation dynamics with statistical confidence inaccessible to direct ab initio simulation. The trained DP model reproduces experimental liquid and glass structure, captures the cooling-rate dependence of the bulk glass transition, and corrects systematic biases in the polyhedral populations predicted by widely used classical force fields. At the free surface, mass density recovers to bulk values over ~10 Å, while local coordination requires a slightly wider subsurface region to fully converge. The outermost layer is oxygen-enriched, exhibits altered polyhedral connectivity with contracted Al–O bonds, and hosts a broad population of under-coordinated motifs (notably AlO 3 and OAl 2 ) whose abundances are governed by glass stability. These under-coordinated surface motifs exhibit distinct vibrational signatures and occur as locally paired Lewis acid and Brønsted base sites consistent with bond-valence compensation, yet remain spatially dispersed rather than aggregating into extended clusters. Despite this pronounced structural heterogeneity, surface relaxation and the glass-transition temperature remain comparable to their bulk counterparts, suggesting that the disordered surface is kinetically stable once formed. Together, these results establish a molecular-level picture of amorphous alumina surfaces and demonstrate the capability of machine-learned potentials to resolve structure–property relationships in disordered oxide interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Structure, bonding and electronic characteristics of amorphous Se

Ovonic threshold switching (OTS) selector can effectively improve the storage density and suppress the leakage current of advanced phase-change memory. As a prototypical OTS material, amorphous GeSe is widely investigated. But the attentions paid to amorphous Se (i.e., the functional constituent in amorphous GeSe) is very limited up to now. Here, in this work, we have explored the structure, bonding and electronic characteristics of amorphous Se using ab initio molecular dynamics simulations. The results reveal that the Se atoms in amorphous Se tend to form the 2-coordinated configurations, and they connect with each other to form the long chains. The fraction of vibrational density of state located in high frequency range is relatively large, and the formation energy of Se-Se bond is as large as 4.44 eV, hinting that the Se-Se bonds in chains possess a high stability. In addition, the mid-gap state related to the OTS behavior is also found in the amorphous Se despite of the small proportion. Our findings enrich the knowledge of the amorphous Se, which contributes to the applications of Se-based OTS selectors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Spectroscopic Investigation into P(NDI2OD-T2) Charge Localization

P(NDI2OD-T2), commonly referred to as N2200, stands out as a promising electron-transporting (n-type) polymer for low-cost, flexible (photo)electrochemical applications due to its reversible two-electron reduction and high electron mobility. UV–vis spectroelectrochemistry in the tetrabutyl ammonium hexafluorophosphate/acetonitrile electrolyte shows two sets of chemically reversible redox signals in the cyclic voltammetry corresponding to the reduction of the neutral polymer film to polaronic and bipolaronic species. These electrochemical signatures suggest a distinct electronic reorganization upon reduction (polaron/bipolaron formation), highlighting the need for molecular-level insights into how charges are accommodated within the polymer backbone. While it has been previously hypothesized that charge predominantly localizes on the naphthalene diimide (NDI) unit during reductive charging, specific changes in atomic environments that confirm this localization have not been characterized in n-type polymers. Herein, we use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe electronic transitions in an electrochemically charged polymer to deduce charge localization. The O K-edge (1s) spectra exhibit two distinct π* peaks; the intensity of the lower-energy π* a peak that corresponds to an excitation to a largely localized carbonyl state decreases with reductive potentials relative to the higher-energy π* b peak. We corroborate this with Raman spectroscopy at different potentials, which shows a decrease in intensity on the C–C/C═C and C═O stretching bands of NDI as well as a red shift of the carbonyl band due to the formation of a polaron on the NDI. Additionally, new Raman active NDI signals associated with elongated C═O and C═C bonds are observed at lower energy during the formation of charged states. Together with theoretical calculations, these findings show that the injected charge spatially localizes on the NDI units and is dominantly distributed on the carbonyl groups. In conclusion, the combination of NEXAFS, optical and vibrational spectroscopies, and theoretical calculations is generalizable to other pi-conjugated polymers and can identify charge localization for the further development of organic semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

The Fraternal Twins of Quartet O4(+)

Eleven stationary geometries of quartet O4(+) have been studied by ab initio methods. The geometries were optimized at the Complete Active Space Self-Consistent Field (CASSCF) level of theory and the energies were calculated by the multiconfigurational second order pertubation method (CASPT2), using Double-Zeta Plus polarization (DZP), Triple-Zeta Plus Double Polarization (TZ2P), average Atomic Natural Orbital (ANO) (5s4p2d) and average ANO (6s5p3d2f) basis sets. The rectangular and trans-planar structures are found to be the most stable, with an energy barrier to conversion between the two at the threshold of dissociation. Both have a delocalized hole and are stable relative to separated 02 and 02(+)by 11.0 and 11.5 kcal/mol for the rectangular and the 2 trans-planar structure, respectively, compared with the experimentally deduced energy in the range of 9.2 to 10.8 kcal/mol. The adiabatic ionization potentials of 04 and 02 are computed to be 11.67 and 12.21 eV, while experimental values are 11.66 and 12.07 eV, respectively. The vibrational frequencies have been computed for all degrees of freedom at the CASSCF level of theory. Symmetry breaking is found to be a particular problem in the computation of the antisymmetric stretch frequency for the delocalized structures at the CASSCF level of theory. Attempts to rectify these problems using the restricted active space self-consistent field (RASSCF) method leads to additional difficulties, but further analysis yields insight into the symmetry breaking and problems with earlier calculations. Finally, a nonorthogonal configuration interaction (CI) calculation based on the interaction of localized CASSCF wave functions using the Complete Active Space State Interation (CASSI) method leads to a balanced treatment of the antisymmetric stretch which is free from symmetry breaking. The study explains the four most prominent absorption frequencies observed in the partially unassigned IR spectrum of O4(+) isolated in solid neon as the antisymmetric OO stretch, and the combination band of the symmetric and antisymmetric 00 stretch of both the rectangular and trans-planar structures.

Lindh, Roland↗

DOE OSTI2020

Structure and properties of densified silica glass: characterizing the order within disorder

The broken symmetry in the atomic-scale ordering of glassy versus crystalline solids leads to a daunting challenge to provide suitable metrics for describing the order within disorder, especially on length scales beyond the nearest neighbor that are characterized by rich structural complexity. Here, we address this challenge for silica, a canonical network-forming glass, by using hot versus cold compression to (i) systematically increase the structural ordering after densification and (ii) prepare two glasses with the same high-density but contrasting structures. The structure was measured by high-energy X-ray and neutron diffraction, and atomistic models were generated that reproduce the experimental results. The vibrational and thermodynamic properties of the glasses were probed by using inelastic neutron scattering and calorimetry, respectively. Traditional measures of amorphous structures show relatively subtle changes upon compacting the glass. The method of persistent homology identifies, however, distinct features in the network topology that change as the initially open structure of the glass is collapsed. The results for the same high-density glasses show that the nature of structural disorder does impact the heat capacity and boson peak in the low-frequency dynamical spectra. Densification is discussed in terms of the loss of locally favored tetrahedral structures comprising oxygen-decorated SiSi 4<:sub> tetrahedra.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Rovibrationally resolved Rayleigh and Raman scattering cross sections for molecular hydrogen

Accurate Rayleigh and Raman scattering cross sections, tensor components, depolarization ratios, and reversal coefficients for all rovibrational transitions within the X1Σg+ ground electronic state of H2 have been calculated. Raman spectra have been generated using these data. A method for calculating Raman scattering cross sections is formulated that is valid below the ionization threshold and in the region containing resonances, which explicitly accounts for all bound and dissociative vibrational levels of the bound intermediate electronic states and approximately accounts for the ionization continuum. A representative set of cross sections is presented for incident photon energies below 15 eV and compared with existing results in the literature where possible. Convergence of our results with an increasing number of bound intermediate electronic states is demonstrated. The accuracy of the Placzek–Teller approximation is discussed. The effect of accounting for the intermediate ionization continuum is investigated. Local thermal equilibrium cross sections are calculated for Rayleigh and Raman scattering. This work represents the most accurate and complete treatment of Raman scattering for molecular hydrogen to date. A total of 9582 Rayleigh and Raman scattering cross sections have been generated and are openly available on Zenodo under an open-source Creative Commons Attribution license at https://zenodo.org/doi/10.5281/zenodo.13441471.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1995

Time-Dependent Photodissociation Regions

We present theoretical models of the time-dependent thermal and chemical structure of molecular gas suddenly exposed to far-ultraviolet (FUV) (6 eV less than hv less than 13.6 eV) radiation fields and the consequent time- dependent infrared emission of the gas. We focus on the response of molecular hydrogen for cloud densities ranging from n = 10(exp 3) to 10(exp 6)/cu cm and FUV fluxes G(sub 0) = 10(exp 3)-10(exp 6) times the local FUV interstellar flux. For G(sub 0)/n greater than 10(exp -2) cu cm, the emergent H(sub 2) vibrational line intensities are initially larger than the final equilibrium values. The H(sub 2) lines are excited by FUV fluorescence and by collisional excitation in warm gas. Most of the H(sub 2) intensity is generated at a characteristic hydrogen column density of N approximately 10(exp 21)/sq cm, which corresponds to an FUV optical depth of unity caused by dust opacity. The time dependence of the H(sub 2) intensities arises because the initial abundances of H(sub 2) at these depths is much higher than the equilibrium values, so that H(sub 2) initially competes more effectively with dust in absorbing FUV photons. Considerable column densities of warm (T approximately 1000) K H(sub 2) gas can be produced by the FUV pumping of H(sub 2) vibrational levels followed by collisional de-excitation, which transfers the energy to heat. In dense (n greater than or approximately 10(exp 5)/cu cm) gas exposed to high (G(sub 0) greater than or approximately 10(exp 4)) fluxes, this warm gas produces a 2-1 S(1)/1-0 S(l) H(sub 2) line ratio of approximately 0.1, which mimics the ratio found in shocked gas. In lower density regions, the FUV pumping produces a pure-fluorescent ratio of approximately 0.5. We also present calculations of the time dependence of the atomic hydrogen column densities and of the intensities of 0 I 6300 A, S II 6730 A, Fe II 1.64 microns, and rotational OH and H20 emission. Potential applications include star-forming regions, clouds near active galactic nuclei, and planetary nebulae. We apply our models to five planetary nebulae and conclude that only BD +30deg3639 shows evidence of enhanced H(sub 2) emission due to (high) nonequilibrium H(sub 2) abundances.

Hollenbach, David↗

DOE OSTI2026

Disorder-induced magnetoelastic behaviors of MnTexSbyBi1-x-y alloys

This dataset contains input and output files from density functional theory (DFT) simulations used to study the disorder-induced magnetoelastic behaviors of MnTexSbyBi1-x-y (0 ≤ x + y ≤ 1) alloys and their binary end members MnTe, MnSb, and MnBi. The alloys adopt the hexagonal NiAs-type (nickeline) structure and span ternary (MnTexSb1-x, MnTexBi1-x, MnBixSb1-x), and quaternary compositions across the full MnTe–MnSb–MnBi composition triangle. For each alloy composition, the dataset provides DFT calculations in three magnetic configurations: A-type antiferromagnetic (AFM), C-type AFM, and ferromagnetic (FM). Every magnetic configuration folder contains the fully relaxed crystal structure (CONTCAR), VASP input parameters (INCAR), and the main VASP output file (OUTCAR), from which total electronic energies, Mn magnetic moments, lattice parameters, and percent volume changes between magnetic states are extracted. These data are used to construct compositional phase diagrams, evaluate thermodynamic stability (formability), and map magnetoelastic responses across the alloy space. For A-type AFM and FM configurations, additional data are provided as follows: (i) FORCE_CONSTANTS and thermal_properties.yaml files at the top level of A-type_AFM/ and FM/ folders — present only for compositions marked with an asterisk (*) in Table I of the main text. These are derived from Phonopy finite-displacement calculations on full disordered 128-atom supercells and provide vibrational free energy, entropy (Svib)contribution from explicit disorder calculations. (Table I of the associated main manuscript) (ii) A VCA/ subfolder within A-type_AFM/ and FM/, containing FORCE_CONSTANTS and thermal_properties.yaml from Virtual Crystal Approximation phonon calculations (without spin-orbit coupling). VCA data are available for all compositions and are used to estimate vibrational contributions to the Gibbs free energy across the full composition space. (iii) A SOC/ subfolder containing CONTCAR, INCAR, and OUTCAR from spin-orbit coupling calculations, providing relativistic corrections to electronic energies and lattice parameters (Tables S2–S3 of the SM, and Table I of the main manuscript). (iv) A SOC/VCA/ subfolder containing FORCE_CONSTANTS and thermal_properties.yaml from VCA phonon calculations performed within the SOC framework, combining relativistic and vibrational thermodynamic corrections. The computed properties are used to map the AFM–FM magnetic crossover near MnTe0.75Sb0.25, demonstrate disorder- and spin-induced phonon broadening, identify a semiconductor-to-metal crossover, and quantify the pronounced magnetoelastic volume response near the magnetic phase boundary.

36 MATERIALS SCIENCE↗

NASA NTRS1993

The quantum dynamics of electronically nonadiabatic chemical reactions

Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally adiabatic functions in various quantum scattering algorithms.

Truhlar, Donald G.↗

DOE OSTI2026

Coherent anti-Stokes Raman scattering with squeezed light: CARS for quantum-enhanced spectroscopy and imaging

We theoretically investigate quantum-enhanced coherent anti-Stokes Raman scattering (CARS) using squeezed light to amplify vibrational transition rates at low photon flux. Quantum sensing approaches are needed for nondestructive nanometrology such as in bioimaging where reduced photodamage is desired while retaining resolution and sensitivity. We analyze both single-mode squeezing applied to the pump field and two-mode squeezing between the pump and Stokes fields. We also show that the ordering of displacement and squeezing operations—whether displacement precedes squeezing or squeezing precedes displacement—has an impact on the resulting CARS transition amplitudes due to a difference in the photon number and the quantum-enhancement coefficients, with the latter offering a stronger enhancement in the case of two modes squeezing of the pump and Stokes under experimentally accessible conditions. Furthermore, our calculations capture these quantum enhancements through the intrinsic photon-number correlations of squeezed light, eliminating the need for interferometric detection or higher pump powers that are otherwise required to reach comparable sensitivities in classical CARS. Finally, we outline a quantum plasmonic extension of our model in which local field enhancements caused by surface plasmon excitation in metallic nanoparticles can be incorporated via mode-selective field amplification factors, offering a pathway toward combining squeezed-light quantum optics with surface-enhanced nanoscale spectroscopy and imaging.

Atomic & molecular structure↗

NASA NTRS1997

The Solar-Stellar Connection (NAG5-6124: SOHO Guest Investigator Program)

The following is a final report from the SOHO Guest Investigator program to use the SUMER far-UV spectrometer to obtain imaging spectroscopy in support of the goals of the so-called "solar-stellar connection." In particular, a major emphasis was utilization of the long-slit time-resolved maps of the solar surface in bright far-UV emission lines to deduce how particular aspects of the temporally and spatially averaged line profiles trace back to individual structural features of the magnetically disturbed outer atmosphere; to help interpret the unresolved line profiles from high quality stellar observations (say, with the Space Telescope Imaging Spectrograph). The researchers served two tours of duty in the SOHO Operations Center as SUMER planners, during which time we conducted an extensive series of observing programs. These can be divided into three general categories: surface mapping, translimb spectroscopy, and active region diagnostics. We have analyzed some of the large volumes of data to the point where we have presented them in poster papers, and in invited papers at national and international meetings. Listed below are the titles of the preliminary publications we have written, including brief abstracts to indicate the main results. (1) Chromospheric structure and Dynamics-- Observations -- The chromosphere is a highly structured dynamic 'layer' of the solar outer atmosphere. Here, not only are the effects of mechanical heating first evident (moving upward in altitude from the deep photosphere), but also the amount of nonradiative energy deposited is far greater than in the albeit much hotter overlying transition region and corona. Further, the chromosphere is by far the thickest zone of the solar atmosphere with respect to the pressure scale height. A major goal of stellar astrophysics is to understand how the chromosphere is heated and why it adopts its peculiar structure. A cursory examination of solar filtergrams and high-resolution movies demonstrates that much of the chromospheric "action" must be occurring on fine spatial scales and short times; particularly in the cell interior transient brightenings, but also in the longer-lived network fragments. That regime of investigation is far removed from what one usually associates with "synoptic" measurements. Nevertheless, synoptic observations of chromospheric indices, filtergrams, and globally-averaged profile parameters not only can provide important insight concerning the crucial role of the cycle-variable part of the solar magnetic field; but they also can forge a key link with analogous measurements of the stars, where often the phenomena can be significantly exaggerated from the solar case, but high spatial resolution reconnaissance is not even a remote possibility. In addition to discussing the synoptic aspects of chromospheric structure and dynamics, I summarized new insights into the general problem of the solar chromosphere that have been obtained recently with the SUMER far-ultraviolet spectrometer on SOHO. (2) CO and the Temperature Structure of the Solar Atmosphere -- The surface layers of the Sun provide a crucial boundary condition for many of the processes that occur in the deep interior. The stratification of the outer solar atmosphere once was thought to be well understood. However, studies of thermally sensitive molecular absorptions in the infrared revealed puzzling anomalies. Strong lines of the CO fundamental vibration-rotation bands near 5 microns showed very cool temperatures at the extreme limb, and remarkable off-limb emissions extending well into the supposedly hot chromosphere. The conflicting pictures of the photosphere/chromosphere interface, from the widely separated wavelength regimes, has raised suspicions that those "layers" of the atmosphere are much more inhomogeneous than previously suspected. One proposal is that the low chromosphere is dominated by cool gas, the "COmosphere," which is threaded by a network of persistent small-scale hot magnetic filaments and occasionally disrupted by localized acoustic disturbances. The COmosphere is capped by the merged fields of the network elements in the chromospheric "canopy." (3) Translimb Spectroscopy with SOHO/SUMER -- We have used SUMER to obtain deep exposures of the 1300-1400 A spectrum, at the extreme limb and off-limb. Previous "translimb" studies in the thermal infrared had revealed remarkable extensions of cold material (T is approximately equal to 3000 K)-traced by carbon monoxide emission lines-into the heart of the hot chromosphere. A main objective of our program was to search for corresponding far-UV signatures of the "thermally-bifurcated" low chromosphere; for example, radiatively fluoresced emissions of the CO A-X 4th-positive system (collisional excitation would be negligible in cold gas). We conducted two separate observing programs with SUMER. Both made use of the 1 inch-diameter circular aperture, translated across the limb in the minimum motor step increments of 0."375, along the central meridian in the Northern polar coronal hole. The first program executed for nine hours beginning 19UT 25 Oct 1996. The full wavelength range was 1340-1400 A. It was recorded in two overlapping segments, placing key regions of the spectrum alternately on the KBr and bare parts of the detector, to help isolate 2nd-order features. Each segment was integrated for 500 s, and 32 pairs were obtained to span a 12" swath centered on the optical limb. The second program was conducted 00-09UT 01 Dec 1996. It consisted of a single wavelength setting (1300-1340 A) with exposure time 500 s, but twice the spatial coverage of the earlier series: 64 steps, for a total displacement of 24". The strong chromospheric resonance lines of atomic oxygen (1302-1305 A) and ionized carbon (1334-1335 A) were observed on the bare part of the MCP camera.

Ayres, Thomas R.↗