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Results for “molecular electronics”
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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Quantum-classical hybrid algorithm for the simulation of all-electron correlation
While chemical systems containing hundreds to thousands of electrons remain beyond the reach of quantum devices, hybrid quantum-classical algorithms present a promising pathway toward a quantum advantage. Hybrid algorithms treat the exponentially scaling part of the calculation-the static correlation-on the quantum computer and the non-exponentially scaling part-the dynamic correlation-on the classical computer. While a variety of algorithms have been proposed, the dependence of many methods on the total wave function limits the development of easy-to-use classical post-processing implementations. Here, we present a novel combination of quantum and classical algorithms, which computes the all-electron energy of a strongly correlated molecular system on the classical computer from the 2-electron reduced density matrix (2-RDM) evaluated on the quantum device. Significantly, we circumvent the wave function in the all-electron calculations by using density matrix methods that only require input of the statically correlated 2-RDM. Although the algorithm is completely general, we test it with two classical density matrix methods, the anti-Hermitian contracted Schrödinger equation (ACSE) and multiconfiguration pair-density functional theories, using the recently developed quantum ACSE method for simulating the statically correlated 2-RDM. Furthermore, we obtain experimental accuracy for the relative energies of all three benzyne isomers and thereby demonstrate the ability of the developed algorithm to achieve chemically relevant and accurate results on noisy intermediate-scale quantum devices.
True molecular conformation and structure determination by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applications
The true molecular conformation and the crystal structure of benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene, 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene were determined ab initio by 3D electron diffraction. All three molecules are remarkable polycyclic aromatic hydrocarbons. The molecular conformation of two of these compounds could not be determined via classical spectroscopic methods due to the large size of the molecule and the occurrence of multiple and reciprocally connected aromatic rings. The molecular structure of the third molecule was previously considered provisional. These compounds were isolated as by-products in the synthesis of similar products and were at the same time nanocrystalline and available only in very limited amounts. 3D electron diffraction data, taken from submicrometric single crystals, allowed for direct ab initio structure solution and the unbiased determination of the internal molecular conformation. Detailed synthetic routes and spectroscopic analyses are also discussed. Based on many-body perturbation theory simulations, benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene may be a promising candidate for triplet–triplet annihilation and 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene may be a promising candidate for intermolecular singlet fission in the solid state.
Design, fabrication and evaluation of a prototype molecular beam gimballed detector, control circuits, and signal processing electronics
Design, development, and evaluation of gimballed system for aligning spacecraft mounted instruments with relative wind
Infrared Line Emission from Molecular Gas Heated by X-Rays and Energetic Electrons
"I propose to carry out a detailed study using infrared observations (and in some cases, optical and ultraviolet observations) of dense interstellar gas exposed to intense fluxes of X-rays and/or energetic electrons. This is undoubtedly the dominant source of line emission for clouds exposed to X-rays from active galactic nuclei, supernova shocks, or embedded X-ray sources (e.g., X-ray binaries), or to high-temperature or relativistic electrons in galaxy clusters, near powerful radio sources, or supernova remnants. Detailed physical and chemical models of such clouds will be used to analyze infrared observations of the Great Annihilator X-ray source in the Galactic Center, cD galaxies in massive cooling flows, and the nuclei of Seyfert galaxies which will be obtained with the Infrared Space Observatory (ISO), UV and optical observations of the Crab Nebula obtained with the Hubble Space Telescope, and ground-based near-infrared observations of Seyfert nuclei. Results from this work will also be of great relevance to observations obtained with the Submillimeter Wave Astronomical Satellite (SWAS). In the first year of funding of this proposal, my chief collaborators (D.J. Hollenbach and A.G.G.M. Tielens, both of NASA Ames Research Center) and I concentrated on completing our models of the physical conditions in, and the resulting line emission from, dense gas irradiated by X-rays. As noted in the original proposal, some important physical processes were not yet thoroughly incorporated into our models at the time of submission. We completed our modeling of the physical conditions and line emission for essentially the entire range of parameter space (five orders of magnitude in X-ray flux to gas density ratio) occupied by typical dense interstellar clouds in which the gas is mostly neutral and X-rays are important for the ionization, chemistry, and thermal balance.
Differences in Electronic Structure of Global Warming Molecules Lead to Different Molecular Properties. Reply to Wallington et al.
No abstract available
Large-Area Heteroepitaxial Nanostructuring of Molecular Semiconductor Films for Enhanced Optoelectronic Response in Flexible Electronics
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Release and Validation of the EPRDATA25 Electron-Photon-Relaxation Library
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Direct Observation of the ππ* to nπ* Transition in 2-Thiouracil via Time-Resolved NEXAFS Spectroscopy
The photophysics of nucleobases has been the subject of both theoretical and experimental studies over the past decades due to the challenges posed by resolving the steps of their radiationless relaxation dynamics, which cannot be described in the framework of the Born–Oppenheimer approximation (BOA). In this context, the ultrafast dynamics of 2-thiouracil has been investigated with a time-resolved NEXAFS study at the Free Electron Laser FLASH. Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS) can be used to observe electronic transitions in ultrafast molecular relaxation. We performed time-resolved UV-pump/X-ray probe absorption measurements at the sulfur 2s (L1) and 2p (L2/3) edges. We are able to identify absorption features corresponding to the S2 (ππ*) and S1 (nπ*) electronic states. We observe a delay of 102 ± 11 fs in the population of the nπ* state with respect to the initial optical excitation and interpret the delay as the time scale for the S2 → S1 internal conversion. We furthermore identify oscillations in the absorption signal that match a similar observation in our previous X-ray photoelectron spectroscopy study on the same molecule.
Dipole moments and transition probabilities of the a 3Sigma(+)g - b 3Sigma(+)u system of molecular hydrogen
Multiconfiguration variational calculations of the electronic wave functions of the a 3Sigma(+)g and b 3Sigma(+)u states of molecular hydrogen are presented, and the electric dipole transition moment between them (of interest in connection with stellar atmospheres and the UV spectrum of the Jovian planets) is obtained. The dipole moment is used to calculate the probabilities of radiative transitions from the discrete vibrational levels of the a 3Sigma(+)g state to the vibrational continuum of the repulsive b 3Sigma(+)u state as functions of the wavelength of the emitted photons. The total transition probabilities and radiative lifetimes of the levels v prime = 0-20 are presented.
Effects of Dimethylamino Functional Group Substitution on the Physical, Structural and Radiolytic Properties of Pyridinium Ionic Liquids
A diverse range of 4-dimethylaminopyridinium (DMAP) bis(trifluoromethylsulfonyl)-amide ionic liquids with specific functionalities (alkyl, alkoxy, hydroxyalkyl and benzyl) were designed, characterized and compared with their pyridinium analogs in terms of their physical and radiolytic properties. The influence of the dimethylamino group on ionic liquid structure was investigated by X-ray diffraction and molecular dynamics simulations. The influence of the electron-donating ability of the dimethylamino-substituted cation is evident in the differences in the electronic density of states between the DMAP and pyridinium ILs. This leads to substantial changes in the radical transients observed in pulse radiolysis of the neat ILs. It was found that the DMAP salts were higher melting, more viscous and less conducting than their pyridinium analogs. However, the DMAP salts exhibited higher thermal stabilities and could therefore be useful for high-temperature applications.
Statistical learning for predicting density–matrix-based electron dynamics
In this study, we consider the problem of learning density-dependent molecular Hamiltonian matrices from time series of electron density matrices, all in the context of Hartree–Fock theory. Prior work developed a solution to this problem for small molecular systems with density and Hamiltonian matrices of size at most 6 × 6. Here, using a battery of techniques, we scale prior methods to larger molecular systems with, for example, 29 × 29 matrices. This includes systems that either have more electrons or are expressed in large basis sets such as 6-311++G**. Scaling the method to larger systems enhances its relevance for realistic applications in chemistry and physics. To achieve this scaling, we apply dimensionality reduction, ridge regression and analytic computation of Hessians. Through the combination of these techniques, we are able to learn Hamiltonians by minimizing an objective function that encodes local propagation error. Importantly, these learned Hamiltonians can then be used to predict electron dynamics for thousands of steps: When we use our learned Hamiltonians to numerically solve the time-dependent Hartree–Fock equation, we obtain predicted dynamics that are in close quantitative agreement with ground truth dynamics. This includes field-off trajectories similar to the training data and field-on trajectories outside of the training data.
Excitation rates in the auroral nitrogen second positive group.
Auroral excitation rates and molecular vibrational tempratures in nitrogen 2PG from Franck-Condon factors obtained from intensity measurements and high resolution absorption spectral data
Stabilizing Ru-Formyl CO 2 Reduction Intermediates by Formation of Lewis Acid–Base Adducts: A Combined 2DIR and NMR Study
This work demonstrates how the stability of a Ru(II) formyl complex (cis-[Ru(bpy) 2 (CO)(CHO)][PF 6 ]), which is known to decarbonylate to form the metal hydride complex, is greatly enhanced by the addition of a Lewis acidic cation (Li + or Mg 2+ ). Multinuclear NMR is used to measure equilibrium constants of adduct formation, and then ultrafast 2DIR spectroscopy is applied to determine how the electronic structure and local molecular dynamics change upon complexation of the formyl ligand with the Lewis acid. We attribute the stabilization of the complex to the formation of a carbene-like structure where the bond strength between the Ru and the formyl group increases. The change in electronic structure is evidenced by steady-state NMR spectroscopy and DFT calculations. 2DIR measurements further confirm both the complexation of the formyl ligand with the Lewis acid and the change in electronic structure, where changes in vibrational frequency, relaxation kinetics, and a slowdown in the time scale of rotation about the metal-formyl bond are observed in the presence of Lewis acids.
Identifying Regimes During Plasma Catalytic Ammonia Synthesis
Herein, we demonstrate that the performance of mesoporous silica SBA-15 and SBA-15-Ag during plasma ammonia synthesis depends on the plasma conditions. At high power, the mesoporous silica SBA-15 without Ag produces the largest amount of ammonia, but the addition of Ag provides a minor benefit at lower powers. Plasma conditions were analyzed through optical emission spectroscopy using N 2 , N 2 + , and NH molecular bands and H α line. Stark broadening of H α line was used to find electron density, and N 2 molecular bands were used to assess N 2 vibrational excitation, important for plasma nitrogen decomposition. At similar input conditions, reactors with SBA-15 have higher electron density and higher N 2 vibrational temperature. Consistent with higher electron density, SBA-15 reactors have stronger N 2 + emission intensity relative to the neutral N 2 . The addition of Ag results in higher N 2 rotational temperature, possibly due to localized heating. From the materials point of view, SBA-15 is a more robust catalyst with good surface area retention after plasma exposure due to the lack of local heating generated when a metal is in the structure. Furthermore, we identify two possible regimes during ammonia synthesis, a metal and a surface-plasma driven. At lower plasma densities, the addition of metal is beneficial, while at higher power and plasma density, the best performance is achieved without the aid of a metal catalyst.
Single-active electron calculations of high-order harmonic generation from valence shells in atoms for quantitative comparison with TDDFT calculations
Not Available
High-throughput ab initio reaction mechanism exploration in the cloud with automated multi-reference validation
Quantum chemical calculations on atomistic systems have evolved into a standard approach to studying molecular matter. These calculations often involve a significant amount of manual input and expertise, although most of this effort could be automated, which would alleviate the need for expertise in software and hardware accessibility. Here, we present the AutoRXN workflow, an automated workflow for exploratory high-throughput electronic structure calculations of molecular systems, in which (i) density functional theory methods are exploited to deliver minimum and transition-state structures and corresponding energies and properties, (ii) coupled cluster calculations are then launched for optimized structures to provide more accurate energy and property estimates, and (iii) multi-reference diagnostics are evaluated to back check the coupled cluster results and subject them to automated multi-configurational calculations for potential multi-configurational cases. All calculations are carried out in a cloud environment and support massive computational campaigns. Key features of all components of the AutoRXN workflow are autonomy, stability, and minimum operator interference. We highlight the AutoRXN workflow with the example of an autonomous reaction mechanism exploration of the mode of action of a homogeneous catalyst for the asymmetric reduction of ketones.
Analytical nonadiabatic coupling and state-specific energy gradient for the crystal field Hamiltonian describing lanthanide single-ion magnets
Paramagnetic molecules with a metal ion as an electron spin center are promising building blocks for molecular qubits and high-density memory arrays. However, fast spin relaxation and decoherence in these molecules lead to a rapid loss of magnetization and quantum information. Nonadiabatic coupling (NAC), closely related to spin-vibrational coupling, is the main source of spin relaxation and decoherence in paramagnetic molecules at higher temperatures. Predicting these couplings using numerical differentiation requires a large number of computationally intensive ab initio or crystal field electronic structure calculations. To reduce computational cost and improve accuracy, we derive and implement analytical NAC and state-specific energy gradient for the ab initio parametrized crystal field Hamiltonian describing single-ion molecular magnets. Our implementation requires only a single crystal field calculation. In addition, the accurate NACs and state-specific energy gradients can be used to model spin relaxation using sophisticated nonadiabatic molecular dynamics, which avoids the harmonic approximation for molecular vibrations. To test our implementation, we calculate the NAC values for three lanthanide complexes. Finally, the predicted values support the relaxation mechanisms reported in previous studies.