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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Modeling Molecules under Pressure with Gaussian Potentials

The computational modeling of molecules under high pressure is a growing research area that augments experimental high-pressure chemistry. Here, a new electronic structure method for modeling atoms and molecules under pressure, Gaussians On Surface Tesserae Simulate HYdrostatic Pressure (GOSTSHYP) approach, is introduced. In this method, a set of Gaussian potentials is distributed evenly on the van der Waals surface of the investigated chemical system, leading to a compression of the electron density and the atomic scaffold. Since no parameters other than pressure need to be specified, GOSTSHYP allows straightforward geometry optimizations and ab initio molecular dynamics simulations of chemical systems under pressure for nonexpert users. In this work, calculated energies, bond lengths, and dipole moments under pressure fall within the range of established computational methods for high-pressure chemistry. A Diels-Alder reaction and the cyclotrimerization of acetylene showcase the ability of GOSTSHYP to model pressure-induced chemical reactions. The connection to mechanochemistry is pointed out.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A Stabilizer Framework for the Contextual Subspace Variational Quantum Eigensolver and the Noncontextual Projection Ansatz

Quantum chemistry is a promising application for noisy intermediate-scale quantum (NISQ) devices. However, quantum computers have thus far not succeeded in providing solutions to problems of real scientific significance, with algorithmic advances being necessary to fully utilize even the modest NISQ machines available today. We discuss a method of ground state energy estimation predicated on a partitioning of the molecular Hamiltonian into two parts: one that is noncontextual and can be solved classically, supplemented by a contextual component that yields quantum corrections obtained via a Variational Quantum Eigensolver (VQE) routine. This approach has been termed Contextual Subspace VQE (CS-VQE); however, there are obstacles to overcome before it can be deployed on NISQ devices. The problem we address here is that of the ansatz, a parametrized quantum state over which we optimize during VQE; it is not initially clear how a splitting of the Hamiltonian should be reflected in the CS-VQE ansätze. We propose a “noncontextual projection” approach that is illuminated by a reformulation of CS-VQE in the stabilizer formalism. This defines an ansatz restriction from the full electronic structure problem to the contextual subspace and facilitates an implementation of CS-VQE that may be deployed on NISQ devices. We validate the noncontextual projection ansatz using a quantum simulator and demonstrate chemically precise ground state energy calculations for a suite of small molecules at a significant reduction in the required qubit count and circuit depth.

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

Generating Protein Structures for Pathway Discovery Using Deep Learning

Resolving the intricate details of biological phenomena at the molecular level is fundamentally limited by both length- and time scales that can be probed experimentally. Molecular dynamics (MD) simulations at various scales are powerful tools frequently employed to offer valuable biological insights beyond experimental resolution. However, while it is relatively simple to observe long-lived, stable configurations of, for example, proteins, at the required spatial resolution, simulating the more interesting rare transitions between such states often takes orders of magnitude longer than what is feasible even on the largest supercomputers available today. One common aspect of this challenge is pathway discovery, where the start and end states of a scientific phenomenon are known or can be approximated, but the mechanistic details in between are unknown. Here, we propose a representation-learning-based solution that uses interpolation and extrapolation in an abstract representation space to synthesize potential transition states, which are automatically validated using MD simulations. The new simulations of the synthesized transition states are subsequently incorporated into the representation learning, leading to an iterative framework for targeted path sampling. Our approach is demonstrated by recovering the transition of a RAS-RAF protein domain (CRD) from membrane-free to interacting with the membrane using coarse-grain MD simulations.

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

Nonempirical Prediction of the Length-Dependent Ionization Potential in Molecular Chains

The ionization potential of molecular chains is well-known to be a tunable nanoscale property that exhibits clear quantum confinement effects. State-of-the-art methods can accurately predict the ionization potential in the small molecule limit and in the solid-state limit, but for intermediate, nanosized systems prediction of the evolution of the electronic structure between the two limits is more difficult. Recently, optimal tuning of range-separated hybrid functionals has emerged as a highly accurate method for predicting ionization potentials. This was first achieved for molecules using the ionization potential theorem (IPT) and more recently extended to solid-state systems, based on an ansatz that generalizes the IPT to the removal of charge from a localized Wannier function. Here, we study one-dimensional molecular chains of increasing size, from the monomer limit to the infinite polymer limit using this approach. By comparing our results with other localization-based methods and where available with experiment, we demonstrate that Wannier-localization-based optimal tuning is highly accurate in predicting ionization potentials for any chain length, including the nanoscale regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy

Metal centers in transition metal–ligand complexes occur in a variety of oxidation states causing their redox activity and therefore making them relevant for applications in physics and chemistry. The electronic state of these complexes can be studied by X-ray absorption spectroscopy, which is, however, due to the complex spectral signature not always straightforward. Here, we study the electronic structure of gas-phase cationic manganese acetylacetonate complexes Mn(acac) 1–3 + using X-ray absorption spectroscopy at the metal center and ligand constituents. The spectra are well reproduced by multiconfigurational wave function theory, time-dependent density functional theory as well as parameterized crystal field and charge transfer multiplet simulations. This enables us to get detailed insights into the electronic structure of ground-state Mn(acac) 1–3 + and extract empirical parameters such as crystal field strength and exchange coupling from X-ray excitation at both the metal and ligand sites. By comparison to X-ray absorption spectra of neutral, solvated Mn(acac) 2,3 complexes, we also show that the effect of coordination on the L 3 excitation energy, routinely used to identify oxidation states, can contribute about 40–50% to the observed shift, which for the current study is 1.9 eV per oxidation state.

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

Reconciling the Different Apparent Decay Pathways for Iron(III) Tetraphenylporphyrin Chloride: Evidence for Excited State Branching

Detailed understanding of the photophysical properties of metalloporphyrins is key to rationally exploiting them in a variety of applications ranging from photocatalysis to opto-magnetics. Previous studies of the ferric-tetraphenylporphyrin chloride have provided contradictory descriptions of the excited state evolution. Optical transient-absorption suggested initial formation of a ππ* excited state, followed by ligand-to-metal charge-transfer (LMCT) from the porphyrin ring and then decay on the ∼2 ps time scale to a metal-centered excited state that had a lifetime of ∼15 ps. In contrast, femtosecond extreme ultraviolet transient-absorption at the Fe M 2,3 -edge, while agreeing on the initial formation of an LMCT state, found evidence that this decayed in ∼2 ps to the ground state. Here, we have used K-edge transient X-ray absorption and X-ray emission, together with time-resolved X-ray solution scattering to explore this system. Based on these data, we propose a new model, consistent with both the earlier and the current data, in which photoexcited FeTPPCl evolves through three different states on the LMCT manifold, with the ∼2 ps decay now seen to involve a branching between return to the ground state (∼70%) and formation of a long-lived LMCT state (∼30%).

Excited states↗
DOE OSTI2020

The Photoactive Excited State of the B 12 -Based Photoreceptor CarH

In this study we have used transient absorption spectroscopy in the UV–visible and X-ray regions to characterize the excited state of CarH, a protein photoreceptor that uses a form of B 12 , adenosylcobalamin (AdoCbl), to sense light. With visible excitation, a nanosecond-lifetime photoactive excited state is formed with unit quantum yield. The time-resolved X-ray absorption near edge structure difference spectrum of this state demonstrates that the excited state of AdoCbl in CarH undergoes only modest structural expansion around the central cobalt, a behavior similar to that observed for methylcobalamin rather than for AdoCbl free in solution. We propose a new mechanism for CarH photoreactivity involving formation of a triplet excited state. This allows the sensor to operate with high quantum efficiency and without formation of potentially dangerous side products. By stabilizing the excited electronic state, CarH controls reactivity of AdoCbl and enables slow reactions that yield nonreactive products and bypass bond homolysis and reactive radical species formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Structure of Sulfuric Acid Solutions Using Pair Distribution Function Analysis

Solvation and mesoscale ordering of sulfuric acid and other strong acid solutions leads to suppressed freezing points and strong rheological changes with varying concentration. While the solid-state structures are well-understood, studies focused on the evolving solvation structure in the solution phase have probed a limited concentration range (~1–6 M). This study applies a total scattering approach in both the wide-angle X-ray scattering (WAXS) and pair distribution function (PDF) regimes to elucidate the evolving solvation structure over its full range of acid concentration (0–18 M). The emergence of a prepeak in the WAXS regime at intermediate concentrations indicates a transition from noninteracting sulfate molecules in the dilute limit to sterically limited sulfates at concentrations near its deep eutectic point. Fits to the PDF data quantify this trend, showing a transition from octahedrally hydrated sulfates up to 6–7 M concentrations, followed by gradual dehydration, and eventually reaching a solution structure similar to that of water-in-salt electrolyte systems at high acid concentrations.

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

Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B 12 Coenzymes Controlled by the Axial Base

Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. Here these data provide insights into the role of the lower axial ligand in modulating the reactivity of B 12 coenzymes.

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

Structural Evolution of Photoexcited Methylcobalamin toward a CarH-like Metastable State: Evidence from Time-Resolved X-ray Absorption and X-ray Emission

CarH is a protein photoreceptor that uses a form of B 12 , adenosylcobalamin (AdoCbl), to sense light via formation of a metastable excited state. Aside from AdoCbl bound to CarH, methylcobalamin (MeCbl) is the only other example – to date – of photoexcited cobalamins forming metastable excited states with lifetimes of nanoseconds or longer. The UV-visible spectra of the excited states of MeCbl and AdoCbl bound to CarH are similar. We have used transient Co K-edge X-ray absorption and X-ray emission spectroscopies in conjunction with transient absorption spectroscopy in the UV–visible region to characterize the excited states of MeCbl. These data show that the metastable excited state of MeCbl has a slightly expanded corrin ring and increased electron density on the cobalt, but only small changes in the axial bond lengths. Finally, this is similar to changes seen previously for CarH, suggesting that MeCbl may be a good model for AdoCbl in CarH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Influence of Electronic Polarization on the Spectral Density

Accurate spectral densities are necessary for computing realistic exciton dynamics and nonlinear optical spectra of chromophores in condensed-phase environments, including multichromophore pigment–protein systems. However, due to the significant computational cost of computing spectral densities from first principles, requiring many thousands of excited-state calculations, most simulations of realistic systems rely on treating the environment as fixed-point charges. In this work, using a number of representative systems ranging from solvated chromophores to the photoactive yellow protein (PYP), we demonstrate that the quantum mechanical (QM) electronic polarization of the environment is key to obtaining accurate spectral densities and line shapes within the cumulant framework. We show that the QM environment can enhance or depress the coupling of fast chromophore degrees of freedom to the energy gap, altering the electronic–vibrational coupling and the resulting vibronic progressions in the absorption spectrum. In analyzing the physical origin of peaks in the spectral density, we identify vibrational modes that couple the electron and the hole as being particularly sensitive to the QM screening of the environment. For PYP, we reveal the need for careful determination of the appropriate QM region to obtain reliable spectral densities. Our findings suggest that the QM polarization of the environment can be crucial not just for excitation energies but also for electronic–vibrational coupling in complex systems with implications for the correct modeling of linear and nonlinear optical spectroscopy in the condensed phase as well as energy transfer in pigment–protein complexes.

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