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All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Wavelength dependent photochemistry of an iron dinitrogen hydride complex via multiple spectroscopies – competing ejection of axial ligands

Nitrogenase (N 2 ase) is a critical enzyme which catalyzes the reaction of N 2 → NH 3 in nature. Studies on the spectroscopy and photochemistry of trans-[Fe II (DMeOPrPE) 2 (N 2 )H][BPh 4 ] (1) and its isotopologues (2–6) provide a possible first step to evaluate the geometries and properties of the real N 2 ase–N 2 structure(s). In this article, we have used FT-IR, FT-Raman, synchrotron-based nuclear resonant vibrational spectroscopy (NRVS) and DFT calculations to examine and assign the normal modes of these complexes. In addition, we have monitored their wavelength dependent photochemistry using mid-IR, near-IR, NRVS, and Mössbauer spectroscopies. Two distinct photolysis pathways are observed with mid-IR at (nominal) 4 K – (1) the cleavage of Fe–N 2 bond in UV or visible light photolyses, which presents a unipolar disappearance of the N 2 peak at 2094 cm −1 and is recombinable; (2) the ejection of trans hydrogen atom with UV irradiation, which has a pair of bipolar peaks with the disappearance of N 2 at 2094 cm −1 and the appearance of a new species at 2056 cm −1 and is non-recombinable. The latter peak is well aligned with the N 2 peak in an Fe I reference complex (7). The combination of mid IR monitored photolysis/recombination and NRVS monitored photolysis form the central evidence for the conclusions in this article. In particular, the Fe II –N 2 and Fe I –H·dissociations are in competition with each other in UV or UV-inclusive photolyses of this dinitrogen hydride complex. In addition, near-IR and Mössbauer also provide consistent evidence about Fe I . This wavelength dependent photochemical work is the first one on a reaction active N 2 ase–N 2 model complex and it also demonstrates the competition ejection between two axial ligands (H· and N 2 ). It offers valuable information for future studies on real N 2 ase–N 2 and its photolysis products.

Dong, Weibing [Liaoning Normal University (China)]↗
DOE OSTI2022

First measurement of the \( {\Lambda}_c^{+} \) → pη ' decay

We present the first measurement of the branching fraction of the singly Cabibbo-suppressed (SCS) decay \( {\Lambda}_c^{+} \) → pη ' with η ' → ηπ + π – , using a data sample corresponding to an integrated luminosity of 981 fb – 1 , collected by the Belle detector at the KEKB e + e – asymmetric-energy collider. A significant \( {\Lambda}_c^{+} \) → pη ' signal is observed for the first time with a signal significance of 5.4 σ . The relative branching fraction with respect to the normalization mode \( {\Lambda}_c^{+} \) → pK – π + is measured to be $$ \frac{\mathcal{B}\left({\Lambda}_c^{+}\to p\eta^{\prime}\right)}{\mathcal{B}\left({\Lambda}_c^{+}\to {pK}^{-}{\pi}^{+}\right)}=\left(7.54\pm 1.32\pm 0.73\right)\times {10}^{-3}, $$ where the uncertainties are statistical and systematic, respectively. Using the world-average value of \( \mathcal{B}\left({\Lambda}_c^{+}\to {pK}^{-}{\pi}^{+}\right) \) = (6 . 28 ± 0 . 32) × 10 – 2 , we obtain $$ \mathcal{B}\left({\Lambda}_c^{+}\to p\eta^{\prime}\right)=\left(4.73\pm 0.82\pm 0.46\pm 0.24\right)\times {10}^{-4}, $$ where the uncertainties are statistical, systematic, and from \( \mathcal{B}\left({\Lambda}_c^{+}\to {pK}^{-}{\pi}^{+}\right) \) , respectively.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Measurements of branching fractions and asymmetry parameters of $ {\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0} $, $ {\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0} $, and $ {\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -} $ decays at Belle

Using a data sample of 980 fb -1 collected with the Belle detector at the KEKB asymmetric-energy e + e - collider, we study the processes of ${\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}$, ${\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0}$, and ${\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -}$ for the first time. The relative branching ratios to the normalization mode of ${\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}$ are measured to be ${\displaystyle \begin{array}{c}\mathcal{B}\left({\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}\right)/\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)=0.18\pm 0.02\left(\mathrm{stat}.\right)\pm 0.01\left(\mathrm{syst}.\right),\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0}\right)/\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)=0.69\pm 0.03\left(\mathrm{stat}.\right)\pm 0.03\left(\mathrm{syst}.\right),\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -}\right)/\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)=0.34\pm 0.06\left(\mathrm{stat}.\right)\pm 0.02\left(\mathrm{syst}.\right),\end{array}}$ where the uncertainties are statistical and systematic, respectively. We obtain ${\displaystyle \begin{array}{c}\mathcal{B}\left({\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}\right)=\left(3.3\pm 0.3\left(\mathrm{stat}.\right)\pm 0.2\left(\mathrm{syst}.\right)\pm 1.0\left(\mathrm{ref}.\right)\right)\times {10}^{-3},\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0}\right)=\left(12.4\pm 0.5\left(\mathrm{stat}.\right)\pm 0.5\left(\mathrm{syst}.\right)\pm 3.6\left(\mathrm{ref}.\right)\right)\times {10}^{-3},\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast 0}\right)=\left(6.1\pm 1.0\left(\mathrm{stat}.\right)\pm 0.4\left(\mathrm{syst}.\right)\pm 1.8\left(\mathrm{ref}.\right)\right)\times {10}^{-3},\end{array}}$ where the uncertainties are statistical, systematic, and from $\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)$, respectively. The asymmetry parameters $\alpha \left({\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}\right)$ and $\alpha \left({\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -}\right)$ are 0.15 ± 0.22(stat.) ± 0.04(syst.) and -0.52 ± 0.30(stat.) ± 0.02(syst.), respectively, where the uncertainties are statistical followed by systematic.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Open quantum systems and Schwinger-Keldysh holograms

We initiate the study of open quantum field theories using holographic methods. Specifically, we consider a quantum field theory (the system) coupled to a holographic field theory at finite temperature (the environment). We investigate the effects of integrating out the holographic environment with an aim of obtaining an effective dynamics for the resulting open quantum field theory. The influence functionals which enter this open effective action are determined by the real-time (Schwinger-Keldysh) correlation functions of the holographic thermal environment. To evaluate the latter, we exploit recent developments, wherein the semiclassical gravitational Schwinger-Keldysh saddle geometries were identified as complexified black hole spacetimes. We compute real-time correlation functions using holographic methods in these geometries, and argue that they lead to a sensible open effective quantum dynamics for the system in question, a question that hitherto had been left unanswered. In addition to shedding light on open quantum systems coupled to strongly correlated thermal environments, our results also provide a principled computation of Schwinger-Keldysh observables in gravity and holography. In particular, these influence functionals we compute capture both the dissipative physics of black hole quasi- normal modes, as well as that of the fluctuations encoded in outgoing Hawking quanta, and interactions between them. We obtain results for these observables at leading order in a low frequency and momentum expansion in general dimensions, in addition to determining explicit results for two dimensional holographic CFT environments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Resonating AdS soliton

The AdS soliton is a nonsingular spacetime that has a flat conformal boundary with a compact S 1 direction. We find a horizonless cohomogeneity-1 metric that describes nonlinear gravitational oscillations of the AdS soliton in five dimensions. We call this spacetime the resonating AdS soliton. This solution is obtained as the nonlinear extension of normal modes of the AdS soliton dual to spin-2 glueball excitations. The boundary energy momentum tensor of the resonating AdS soliton has time periodic components, and it is interpreted as a coherently excited state in the dual field theory. Physical quantities of the resonating AdS soliton are multivalued at a fixed energy, suggesting a transition between different frequency solutions. The energy of the resonating AdS soliton is higher than that of the undeformed AdS soliton, in accordance with the positive energy conjecture proposed by Horowitz and Myers.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Precise measurements of branching fractions for $ {\mathrm{D}}_{\mathrm{s}}^{+} $ meson decays to two pseudoscalar mesons

We measure the branching fractions for seven $D$$^{+}_{s}$ two-body decays to pseudo-scalar mesons, by analyzing data collected at √s = 4.178 ~ 4.226 GeV with the BESIII detector at the BEPCII collider. The branching fractions are determined to be $$ {\displaystyle \begin{array}{c}\mathcal{B}\left({D}_s^{+}\to {K}^{+}\eta \hbox{'}\right)=\left(2.68\pm 0.17\pm 0.17\pm 0.08\right)\times {10}^{-3},\\ {}\mathcal{B}\left({D}_s^{+}\to \eta \hbox{'}{\pi}^{+}\right)=\left(37.8\pm 0.4\pm 2.1\pm 1.2\right)\times {10}^{-3},\\ {}\mathcal{B}\left({D}_s^{+}\to {K}^{+}\eta \right)=\left(1.62\pm 0.10\pm 0.03\pm 0.05\right)\times {10}^{-3},\\ {}\mathcal{B}\left({D}_s^{+}\to \eta {\pi}^{+}\right)=\left(17.41\pm 0.18\pm 0.27\pm 0.54\right)\times {10}^{-3},\\ {}\mathcal{B}\left({D}_s^{+}\to {K}^{+}{K}_S^0\right)=\left(15.02\pm 0.10\pm 0.27\pm 0.47\right)\times {10}^{-3},\\ {}\mathcal{B}\left({D}_s^{+}\to {K}_S^0{\pi}^{+}\right)=\left(1.109\pm 0.034\pm 0.023\pm 0.035\right)\times {10}^{-3},\\ {}\mathcal{B}\left({D}_s^{+}\to {K}^{+}{\pi}^0\right)=\left(0.748\pm 0.049\pm 0.018\pm 0.035\right)\times {10}^{-3},\end{array}} $$ B D s + → K + η ' = 2.68 ± 0.17 ± 0.17 ± 0.08 × 10 - 3 , B D s + → η ' π + = 37.8 ± 0.4 ± 2.1 ± 1.2 × 10 - 3 , B D s + → K + η = 1.62 ± 0.10 ± 0.03 ± 0.05 × 10 - 3 , B D s + → η π + = 17.41 ± 0.18 ± 0.27 ± 0.54 × 10 - 3 , B D s + → K + K S 0 = 15.02 ± 0.10 ± 0.27 ± 0.47 × 10 - 3 , B D s + → K S 0 π + = 1.109 ± 0.034 ± 0.023 ± 0.035 × 10 - 3 , B D s + → K + π 0 = 0.748 ± 0.049 ± 0.018 ± 0.035 × 10 - 3 , where the first uncertainties are statistical, the second are systematic, and the third are from external input branching fraction of the normalization mode $ {D}_s^{+} $ D s + → K + K - π + . Precision of our measurements is significantly improved compared with that of the current world average values.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Measurements of the branching fractions of ${\Xi }_{c}^{+}\to {\Sigma }^{+}{K}_{S}^{0}$, ${\Xi }_{c}^{+}\to {\Xi }^{0}{\pi }^{+}$, and ${\Xi }_{c}^{+}\to {\Xi }^{0}{K}+$ at Belle and Belle II

Using 983.0 fb −1 and 427.9 fb −1 data samples collected with the Belle and Belle II detectors at the KEKB and SuperKEKB asymmetric energy e + e − colliders, respectively, we present studies of the Cabibbo-favored ${\Xi }_{c}^{+}$ decays ${\Xi }_{c}^{+}\to {\Sigma }^{+}{K}_{S}^{0}$ and ${\Xi }_{c}^{+}\to {\Xi }^{0}{\pi }^{+}$, and the singly Cabibbo-suppressed decay ${\Xi }_{c}^{+}\to {\Xi }^{0}{K}^{+}$. The ratios of branching fractions of ${\Xi }_{c}^{+}\to {\Sigma }^{+}{K}_{S}^{0}$ and ${\Xi }_{c}^{+}\to {\Xi }^{0}{K}^{+}$ relative to that of ${\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+}$ are measured for the first time, while the ratio $\mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{0}{\pi }^{+})/\mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+})$ is also determined and improved by an order of magnitude in precision. The measured branching fraction ratios are $\begin{array}{c}\frac{\mathcal{B}\left({\Xi }_{c}^{+}\to {\Sigma }^{+}{K}_{S}^{0}\right)}{\mathcal{B}\left({\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+}\right)}=0.067\pm 0.007\pm 0.003,\\ \frac{\mathcal{B}\left({\Xi }_{c}^{+}\to {\Xi }^{0}{\pi }^{+}\right)}{\mathcal{B}\left({\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+}\right)}=0.251\pm 0.005\pm 0.010,\\ \frac{\mathcal{B}\left({\Xi }_{c}^{+}\to {\Xi }^{0}{K}^{+}\right)}{\mathcal{B}\left({\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+}\right)}=0.017\pm 0.003\pm 0.001.\end{array}$ Additionally, the ratio $\mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{0}{K}^{+})/\mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{0}{\pi }^{+})$ is measured to be 0.068 ± 0.010 ± 0.004. Here, the first and second uncertainties are statistical and systematic, respectively. Multiplying the ratios by the branching fraction of the normalization mode, $\mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+})=(2.9\pm 1.3)%$, we obtain the following absolute branching fractions $\begin{array}{c}\mathcal{B}({\Xi }_{c}^{+}\to {\Sigma }^{+}{K}_{S}^{0})=(0.194\pm 0.021\pm 0.009\pm 0.087)\text{%},\\ \mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{0}{\pi }^{+})=(0.728\pm 0.014\pm 0.027\pm 0.326)\text{%},\\ \mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{0}{K}^{+})=(0.049\pm 0.007\pm 0.003\pm 0.022)\text{%},\end{array}$ where the third uncertainties are from $\mathcal{B}({\Xi }_{c}^{+}\to {\Xi }^{-}{\pi }^{+}{\pi }^{+})$.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Black hole scattering and partition functions

When computing the ideal gas thermal canonical partition function for a scalar outside a black hole horizon, one encounters the divergent single-particle density of states (DOS) due to the continuous nature of the normal mode spectrum. Recasting the Lorentzian field equation into an effective 1D scattering problem, we argue that the scattering phases encode non-trivial information about the DOS and can be extracted by “renormalizing” the DOS with respect to a reference. This defines a renormalized free energy up to an arbitrary additive constant. Interestingly, we discover that the 1-loop Euclidean path integral, as computed by the Denef-Hartnoll-Sachdev formula, fixes the reference free energy to be that on a Rindler-like region, and the renormalized DOS captures the quasinormal modes for the scalar. We support these claims with the examples of scalars on static BTZ, Nariai black holes and the de Sitter static patch. For black holes in asymptotically flat space, the renormalized DOS is captured by the phase of the transmission coefficient whose magnitude squared is the greybody factor. We comment on possible connections with recent works from an algebraic point of view.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Q-balls meet fuzzballs: non-BPS microstate geometries

We construct a three-parameter family of non-extremal microstate geometries, or “microstrata”, that are dual to states and deformations of the D1-D5 CFT. These families are non-extremal analogues of superstrata. We find these microstrata by using a Q-ball-inspired Ansatz that reduces the equations of motion to solving for eleven functions of one variable. We then solve this system both perturbatively and numerically and the results match extremely well. We find that the solutions have normal mode frequencies that depend upon the amplitudes of the excitations. We also show that, at higher order in perturbations, some of the solutions, having started with normalizable modes, develop a “non-normalizable” part, suggesting that the microstrata represent states in a perturbed form of the D1-D5 CFT. This paper is intended as a “Proof of Concept” for the Q-ball-inspired approach, and we will describe how it opens the way to many interesting follow-up calculations both in supergravity and in the dual holographic field theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Dissipation in open holography

We exploit the holographic realization of a conformal theory coupled to an external bath realized via a double trace deformation and its gravity dual in terms of transparent boundary conditions in order to map out some basic dissipative properties of this simple open holographic system. In particular, we determine the energy transmission coefficient across the boundary, discover a novel duality relating weak and strong coupling to the external bath, and quantify the dissipation in the system by working out the quasi normal modes.

AdS-CFT correspondence↗
DOE OSTI2020

Comparison of Surface Tension Generation Methods in Smoothed Particle Hydrodynamics for Dynamic Systems

Developing robust numerical models of dynamic surface tension dominated multiphase systems is an ongoing challenge, especially in scenarios with large density and viscosity ratios. This is critical to the design and understanding of various physical and engineering systems, such as fluidized beds, fuel injectors, and drug delivery schemes. Much of the computational work in surface tension dominated multiphase flows has employed the continuum surface force method (CSF) of Brackbill et al. [1], which recasts surface tension from a surface force to a volumetric force that can be imposed in the vicinity of an interface. The CSF method produces accurate results across a variety of systems, however it relies on the identication of surface normals, which can be unreliable under certain conditions. Alternative methods of simulating surface tension have been proposed. Here the advantages and disadvantages of the CSF method in comparison to a pairwise forces (PF) method proposed by Tartakovsky and Panchenko [2] are explored. The CSF and PF methods are used in a smoothed particle hydrodynamics (SPH) framework to model dynamic systems. Results are compared to existing test cases from the literature and to analytic solutions derived from fundamental normal mode behavior of bubbles and droplets. A physical system for which the PF method is more stable and physically appropriate than the CSF method is identied.

smoothed particle hydrodynamics, multiphase flow↗
DOE OSTI2021

Investigating the non-classical M-H 2 bonding in OsClH 3 (PPh 3 ) 3

Dihydrogen ligation to metal centers results in a wide range of metal-hydrogen interactions. Compounds containing non-classical dihydrogen ligands in which the H-H contacts are significantly longer than the 0.74 A distance found in solid H 2 are classified as Kubas-like compounds, stretched dihydrogen ligands, or compressed dihydrides, depending on the H-H contact length. Compounds containing stretched dihydrogen and compressed dihydride ligands are somewhat rare. Developing a more complete understanding of the metal-hydrogen and hydrogen-hydrogen interactions in these species may provide insights into the mechanisms for the oxidative addition reaction and hydrogen storage. Here, we use diffraction and inelastic neutron scattering (INS) measurements, paired with both molecular and solid-state density functional theory (DFT), to fully characterize the nature of the metal-hydrogen and hydrogen-hydrogen interactions in a previously reported compound, OsClH 3 (PPh 3 ) 3 . In that report, the H-H distance was measured as 1.48(2) A by single-crystal neutron diffraction and was described as a "stretched" dihydrogen. The INS-generated phonon density of states is well described by the DFT calculations, including those normal modes dominated by the vibrational motions of the three Os-ligated hydrogen atoms. Additionally, the resulting calculated electron charge density landscape indicates that there is no remnant bonding character between the Os-ligated hydrogen atoms in the compound. Based on these findings, we update the understanding of the metal-hydrogen bonding in this complex and reclassify it as a compressed dihydride. As such, OsClH 3 (PPh 3 ) 3 represents a rare example of a non-classical compressed dihydride species.

08 HYDROGEN↗
DOE OSTI2021

Experimental and calculated infrared spectra of disubstituted naphthoquinones

In recent years there has been interest in incorporating substituted 1,4-naphthoquinones (NQs) into the A 1 binding site in photosystem I (PSI) photosynthetic protein complexes. This interest in part stems from the considerably altered bioenergetics of electron transfer that occur in PSI with such substitutions. Time resolved FTIR studies of PSI complexes with disubstituted NQs incorporated have and currently are being undertaken, and with this in mind it is worth considering FTIR absorption spectra of these disubstituted NQs in solution. Here we present FTIR absorbance spectra for 2-bromo-3-methyl-1,4-naphthoquinone (BrMeNQ), 2-chloromethyl-3-methyl-1,4-naphthoquinone (CMMeNQ) and 2-ethylthio-3-methyl-1,4-naphthoquinone (ETMeNQ) in tetrahydrofuran (THF). The FTIR spectra of these di-substituted naphthoquinones (NQs) were compared to FTIR spectra of 2-methyl-3-phytyl-1,4-naphthoquinone [phylloquinone (PhQ)], 2,3-dimethyl-1,4-naphthoquinone (DMNQ), and 2-methyl-1,4-naphthoquinone (2MNQ). To aid in the assignment of bands in the experimental spectra, density functional theory (DFT) based vibrational frequency calculations for all the substituted NQs in solution were undertaken. The calculated and experimental spectra agree well. By calculating normal mode potential energy distributions, unambiguous quantitative band assignments were made. The calculated and experimental spectra together make predictions about what may be observable in time resolved FTIR difference spectra obtained using PSI with the different NQs incorporated. As a result, time resolved FTIR difference spectra are presented that support these predictions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Lectures on statistical mechanics

Presented here is a transcription of the lecture notes from Professor Allan N. Kaufman’s graduate statistical mechanics course Physics 212A and 212B at the University of California Berkeley from the 1972–1973 academic year. 212A addressed equilibrium statistical mechanics with topics: fundamentals (micro-canonical and sub-canonical ensembles, adiabatic law and action conservation, fluctuations, pressure, and virial theorem), classical fluids and other systems (equation of state, deviations from ideality, virial coefficients and van der Waals potential, canonical ensemble and partition function, quasistatic evolution, grand-canonical ensemble and partition function, chemical potential, simple model of a phase transition, quantum virial expansion, numerical simulation of equations of state, and phase transition), chemical equilibrium (systems with multiple species and chemical reactions, law of mass action, Saha equation, chemical equilibrium including ionization and excited states), and long-range interactions (including Coulomb, dipole, and gravitational interactions, Debye–Hückel theory, and shielding). 212B addressed nonequilibrium statistical mechanics with topics: fundamentals (definitions: realizations, moments, characteristic function, and discrete variables), Brownian motion (Langevin equation, fluctuation–dissipation theorem, spatial diffusion, Boltzmann’s H-theorem), Liouville and Klimontovich equations, Landau equation (derivation, elaboration, and H-theorem, and irreversibility), Markov processes and Fokker–Planck equation (derivations of the Fokker–Planck equation and a master equation), linear response and transport theory (linear Boltzmann equation, linear response theory of Kubo and Mori, relation of entropy production to electrical conductivity, transport relations and coefficients, normal mode solutions of the transport equations, sketch of a generalized Langevin equation method for transport theory), and an introduction to nonequilibrium quantum statistical mechanics.

plasma dynamics↗
DOE OSTI2024

Effects of Structural Constraints on Excited-State Properties in Dimeric Cu(I) Diimine Complexes

Copper(I) bis-diimine complexes have played important roles in light-activated processes that can lead to their potential applications in photocatalysis and chemical sensing. Their metal-to-ligand charge-transfer (MLCT) excited-state properties are tunable by various structural factors. Dimeric Cu(I) complexes with connecting diimine derivative ligands offer another structural tuning platform for the excited-state properties. Here, we investigate excited-state properties in two covalently connected dimeric Cu(I)'s with varying structural constraints exerted by the number of carbons in the polyethylene bridge (C0 and C4) connecting the two copper(I) diimine moieties. An interesting feature of Cu(I) diimine complexes is their ability to flatten following a photoinduced structural change. Herein, we observe larger structural constraints and more structural rearrangement required upon excitation of the longer bridged complex C4 to achieve a conformation toward a more flattened tetrahedral coordination geometry compared to the shorter bridged C0. Vibrational wavepacket analysis of these complexes further supports the effect of these structural constraints where we observe a more rapid dephasing of the C0 complex, as opposed to the C4 complex, despite similar normal mode vibrations. The experimental results were supplemented by TDDFT calculations. In conclusion, the studies provide insight into using metal-metal interactions through constraints to tune excited-state dynamics and pathways.

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

Ab Initio Study of Vibronic and Magnetic 5f-to-5f and Dipole-Allowed 5f-to-6d and Charge-Transfer Transitions in [UX 6 ] n – (X = Cl, Br; n = 1, 2)

The absorption spectra of the octahedral [UX 6 ] n– (X = Cl, Br; n = 1, 2) complexes in the near-infrared (NIR) and UV–vis spectral regions were studied theoretically, using a relativistic restricted active space second-order perturbation theory (RASPT2) wavefunction framework, with the spin–orbit (SO) coupling treated by state interaction, in conjunction with Kohn–Sham density functional theory calculations for determining the vibrational normal modes. The electric-dipole-allowed ligand-to-metal charge-transfer (LMCT) and 5f-to-6d transitions, and the electric-dipole-forbidden 5f-to-5f ligand field (LF) transitions, are thereby obtained within the same theoretical framework. For the 5f-to-5f LF transitions, the observed absorption intensity is mostly due to vibronic coupling with low-energy electric-dipole-allowed transitions, but in some cases, the magnetic dipole intensity of the purely electronic transition has comparable intensity to the vibronic transitions. Here, experimental LF spectra of 5f 2 open-shell systems have been reported decades back, but ab initio calculations of their vibronic intensity have not yet been reported in the literature. Although the LF spectra for the 5f 2 systems can be assigned in detail, based on the calculations, the spectra are very complex and the underlying electronic states are strongly multiconfigurational. Therefore, the usefulness of the LF spectra beyond serving as a “fingerprint” of the LF and the metal oxidation state appears to be limited.

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

Capturing Deuteration Effects in a Molecular Mechanics Force Field: Deuterated THF and the THF–Water Miscibility Gap

Deuteration is a common chemical modification used in conjunction with experiments such as neutron scattering, NMR, and Fourier-transform infrared for the study of molecular systems. Under the Born–Oppenheimer (BO) approximation, while the underlying potential energy surface remains unchanged by isotopic substitutions, isotopic substitution still alters intramolecular vibrations, which in turn may alter intermolecular interactions. Molecular mechanics (MM) force fields used in classical molecular dynamics simulations are assumed to represent local approximations of the BO potential energy surfaces, and hence, MD simulations using simple isotopic mass substitutions should capture BO-compatible isotope effects. However, standard MM force-field parameterizations do not directly fit to the local harmonic quantum mechanical (QM) Hessian that describes the BO surface, but rather to QM normal-modes and/or mass-dependent internal-coordinate derived distortion energies. In this study, using tetrahydrofuran (THF)–water mixtures as our model system, we show that not only does a simple mass-substitution approach fail to capture an experimentally characterized deuteration effect (the loss of the closed-loop miscibility gap associated with the complete deuteration of THF) but also it is necessary to generate new MM force-field parameters that correctly describe isotopic dependent vibrations to capture the experimental deuteration effect. We show that the origin of this failure is a result of using mass-dependent features to fit the THF MM force field, which unintentionally biases the bonded terms of the force field to represent only the isotopologue used during the original force-field parameterization. In addition, we make use of our isotopologue-corrected force field for D 8 THF to examine the molecular origins of the isotope-dependent loss of the THF–water miscibility gap.

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

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state. Time-resolved X-ray absorption studies showed shortening of C–C bonds and increasing diffraction densities, thought to evidence a liquid or glassy carbon state, respectively. Nevertheless, none of these experiments provided information on the electronic structure of the proposed liquid state. Herein, we report the results of time-resolved resonant inelastic X-ray scattering (RIXS) and time-resolved X-ray emission spectroscopy (XES) studies on amorphous carbon (a-C) and ultrananocrystalline diamond (UNCD) as a function of delay time between the irradiating pulse and X-ray probe. For both a-C and UNCD, we attribute decreases in RIXS or XES signals to transition blocking, relaxation, and finally, ablation. Increased signal at 20 ps following the irradiation of the UNCD is attributed to the probable formation of nanoscale structures in the ablation plume. Further, differences in the amount of signal observed between a-C and UNCD are explained by the difference in sample thickness and, specifically, incomplete melting of the UNCD film. Comparisons to spectral simulations based on MD trajectories at extreme conditions indicate that the carbon state in our experiments is crystalline. Normal mode analysis confirmed that symmetrical bending or stretching of the C–C bonds in the diamond lattice results in XES spectra with small intensity differences. Overall, we observed no evidence of melting to a liquid state, as determined by the lack of changes in the spectral properties for up to 100 ps delays following the melting pulses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗