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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Characterization of light-induced potentials in the strong-field dissociation of O 2 +

In this work, we investigate theoretically the imprints of light-induced potentials (LIPs) on the dissociation dynamics of O 2 + molecular ions, as observable in angle-resolved fragment kinetic-energy-release (KER) spectra. Following the vibrational and rotational dynamics of the initial pump-laser-excited cationic nuclear wave packet, while accounting for the dipole coupling between the O 2 + ( a 4 Π u ) and O 2 + ( f 4 Π g ) electronic states in 800-nm 40-fs probe-laser pulses with peak intensities between 10 13 and 10 14 W / cm 2 , we calculate angle-resolved KER spectra which reveal characteristic energy- and angle-dependent fringe structures. These fringes shift downward in energy as the molecular alignment angle θ relative to the probe-pulse polarization direction increases from 0 to π / 2 . The angle-dependent shifts in the KER fringes increase for larger probe-pulse peak intensities and follow the angle and light-wave-intensity dependence of the vibrational spectrum in the associated Floquet bond-hardening well, which is a manifestation of transient O 2 + nuclear-probability trapping in the LIP during dissociation. By examining the rovibrational dynamics of the dissociating molecular cation near the light-induced conical intersection (LICI) in the cationic LIP surface at θ = π / 2 , we identify related angle-dependent structures in the KER spectra, suggesting a means for assessing the significance of LICIs in molecular dissociation pathways.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Nonadiabatic couplings from a variational excited state method based on constrained DFT

Excited Costrained Density Functional Theory (XCDFT) is a variational excited state method that extends ground state DFT to the computation of low-lying excited states. It borrows much of the machinery of Constrained DFT (CDFT) with a crucial difference: the constraint imposes a population of one electron in the Hilbert space spanned by the virtuals of a reference ground state. Here, we present theory and implementation for evaluating nonadiabatic coupling vectors (NACVs) between the first excited state computed with XCDFT and the ground state. Our NACVs are computed analytically using density functional perturbation theory with a formalism that is general enough that could be applied to CDFT diabatic states. We showcase the new method with pilot NACV calculations for the conical intersection in H 3 , the avoided crossing in selenoacrolein, and the NACV magnitudes in azobenzene. Despite complications from the nonorthogonality of the wavefunctions, XCDFT’s energy surfaces and NACVs reproduce benchmark values and respect known sum rules within a reasonable degree. This shows that XCDFT is a viable method for nonadiabatic dynamics simulations.

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

First-principles study of the surface properties of uranium carbides

Uranium carbides have attracted renewed interest as advanced nuclear fuels for Generation IV reactors. As an important property required for gas bubble modeling in nuclear fuels, the surface energy of uranium carbides is scarce in literature. In this work, we study the surface properties of uranium carbides by first-principles density functional theory calculations. Surface orientations with maximum Miller index up to 3, 2 and 2 are investigated for UC, U 2 C 3 and α-UC 2 , respectively. By studying the effects of surface termination and chemical potential on surface energy, we identify the factors that determines the surface stability. From the calculated surface energies, the surface properties of uranium carbide single crystals are obtained from Wulff construction, including equilibrium morphology, dominant surface orientation and area weighted surface energy.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Revealing CO 2 dissociation pathways at vicinal copper (997) interfaces

Size- and shape-tailored copper (Cu) nanocrystals can offer vicinal planes for facile carbon dioxide (CO 2 ) activation. Despite extensive reactivity benchmarks, a correlation between CO 2 conversion and morphology structure has not yet been established at vicinal Cu interfaces. Herein, ambient pressure scanning tunneling microscopy reveals step-broken Cu nanocluster evolutions on the Cu(997) surface under 1 mbar CO 2 (g). The CO 2 dissociation reaction produces carbon monoxide (CO) adsorbate and atomic oxygen (O) at Cu step-edges, inducing complicated restructuring of the Cu atoms to compensate for increased surface chemical potential energy at ambient pressure. The CO molecules bound at under-coordinated Cu atoms contribute to the reversible Cu clustering with the pressure gap effect, whereas the dissociated oxygen leads to irreversible Cu faceting geometries. Synchrotron-based ambient pressure X-ray photoelectron spectroscopy identifies the chemical binding energy changes in CO-Cu complexes, which proves the characterized real-space evidence for the step-broken Cu nanoclusters under CO(g) environments. Our in situ surface observations provide a more realistic insight into Cu nanocatalyst designs for efficient CO 2 conversion to renewable energy sources during C 1 chemical reactions.

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

Excited state dynamics of cis , cis -1,3-cyclooctadiene: UV pump VUV probe time-resolved photoelectron spectroscopy

We present UV pump, vacuum ultraviolet probe time-resolved photoelectron spectroscopy measurements of the excited state dynamics of cis,cis-1,3-cyclooctadiene. A 4.75 eV deep UV pump pulse launches a vibrational wave packet on the first electronically excited state, and the ensuing dynamics are probed via ionization using a 7.92 eV probe pulse. The experimental results indicate that the wave packet undergoes rapid internal conversion to the ground state in under 100 fs. Comparing the measurements with electronic structure and trajectory surface hopping calculations, we are able to interpret the features in the measured photoelectron spectra in terms of ionization to several states of the molecular cation.

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

Diffusion quantum Monte Carlo approach to the polaritonic ground state

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent and active fields that connects the communities of chemistry and quantum optics. Modeling of such polaritonic phenomena using ab initio approaches calls for new methodologies, leading to the reinvention of many commonly used electronic structure methods, such as Hartree-Fock, density functional, and coupled cluster theories. Here in this work, we explore the formally exact diffusion quantum Monte Carlo approach to obtain numerical solutions to the polaritonic ground state during the dissociation of the H 2 molecular system. Here, we examine various electron-nuclear-photon properties throughout the dissociation, such as changes to the minimum of the cavity Born-Oppenheimer surface, the localization of the electronic wave function, and the average mode occupation. Finally, we directly compare our results to that obtained with state-of-the-art, yet approximate, polaritonic coupled cluster approaches.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Excited-state dynamics of CH 2 I 2 and CH 2 IBr studied with UV-pump VUV-probe momentum-resolved photoion spectroscopy

We perform time-resolved ionization spectroscopy measurements of the excited state dynamics of CH 2 I 2 and CH 2 IBr following photoexcitation in the deep UV. The fragment ions produced by ionization with a vacuum-ultraviolet probe pulse are measured with velocity map imaging, and the momentum resolved yields are compared with trajectory surface hopping calculations of the measurement observable. Together with recent time-resolved photoelectron spectroscopy measurements of the same dynamics, these results provide a detailed picture of the coupled electronic and nuclear dynamics involved. Overall, our measurements highlight the non-adiabatic coupling between electronic states, which leads to notable differences in the dissociation dynamics for the two molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Comparing (stochastic-selection) ab initio multiple spawning with trajectory surface hopping for the photodynamics of cyclopropanone, fulvene, and dithiane

Ab Initio Multiple Spawning (AIMS) simulates the excited-state dynamics of molecular systems by representing nuclear wavepackets in a basis of coupled traveling Gaussian functions, called trajectory basis functions (TBFs). New TBFs are spawned when nuclear wavepackets enter regions of strong nonadiabaticity, permitting the description of non-Born–Oppenheimer processes. The spawning algorithm is simultaneously the blessing and the curse of the AIMS method: it allows for an accurate description of the transfer of nuclear amplitude between different electronic states, but it also dramatically increases the computational cost of the AIMS dynamics as all TBFs are coupled. Recently, a strategy coined stochastic-selection AIMS (SSAIMS) was devised to limit the ever-growing number of TBFs and tested on simple molecules. In this work, we use the photodynamics of three different molecules—cyclopropanone, fulvene, and 1,2-dithiane—to investigate (i) the potential of SSAIMS to reproduce reference AIMS results for challenging nonadiabatic dynamics, (ii) the compromise achieved by SSAIMS in obtaining accurate results while using the smallest average number of TBFs as possible, and (iii) the performance of SSAIMS in comparison to the mixed quantum/classical method trajectory surface hopping (TSH)—both in terms of its accuracy and computational cost. We show that SSAIMS can accurately reproduce the AIMS results for the three molecules considered at a much cheaper computational cost, often close to that of TSH. We deduce from these tests that an overlap-based criterion for the stochastic-selection process leads to the best agreement with the reference AIMS dynamics for the smallest average number of TBFs.

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

Nonadiabatic dynamics with classical trajectories: The problem of an initial coherent superposition of electronic states

Advances in coherent light sources and development of pump–probe techniques in recent decades have opened the way to study electronic motion in its natural time scale. When an ultrashort laser pulse interacts with a molecular target, a coherent superposition of electronic states is created and the triggered electron dynamics is coupled to the nuclear motion. A natural and computationally efficient choice to simulate this correlated dynamics is a trajectory-based method where the quantum-mechanical electronic evolution is coupled to a classical-like nuclear dynamics. These methods must approximate the initial correlated electron–nuclear state by associating an initial electronic wavefunction to each classical trajectory in the ensemble. Different possibilities exist that reproduce the initial populations of the exact molecular wavefunction when represented in a basis. We show that different choices yield different dynamics and explore the effect of this choice in Ehrenfest, surface hopping, and exact-factorization-based coupled-trajectory schemes in a one-dimensional two-electronic-state model system that can be solved numerically exactly. Furthermore, this work aims to clarify the problems that standard trajectory-based techniques might have when a coherent superposition of electronic states is created to initialize the dynamics, to discuss what properties and observables are affected by different choices of electronic initial conditions and to point out the importance of quantum-momentum-induced electronic transitions in coupled-trajectory schemes.

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

Machine learning with bond information for local structure optimizations in surface science

Local optimization of adsorption systems inherently involves different scales: within the substrate, within the molecule, and between the molecule and the substrate. In this work, we show how the explicit modeling of different characteristics of the bonds in these systems improves the performance of machine learning methods for optimization. Furthermore, we introduce an anisotropic kernel in the Gaussian process regression framework that guides the search for the local minimum, and we show its overall good performance across different types of atomic systems. The method shows a speed-up of up to a factor of two compared with the fastest standard optimization methods on adsorption systems. Additionally, we show that a limited memory approach is not only beneficial in terms of overall computational resources but can also result in a further reduction of energy and force calculations.

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

On the Dynamics of the Carbon–Bromine Bond Dissociation in the 1-Bromo-2-Methylnaphthalene Radical Anion

This paper studies the mechanism of electrochemically induced carbon–bromine dissociation in 1-Br-2-methylnaphalene in the reduction regime. In particular, the bond dissociation of the relevant radical anion is disassembled at a molecular level, exploiting quantum mechanical calculations including steady-state, equilibrium and dissociation dynamics via dynamic reaction coordinate (DRC) calculations. DRC is a molecular-dynamic-based calculation relying on an ab initio potential surface. This is to achieve a detailed picture of the dissociation process in an elementary molecular detail. From a thermodynamic point of view, all the reaction paths examined are energetically feasible. The obtained results suggest that the carbon halogen bond dissociates following the first electron uptake follow a stepwise mechanism. Indeed, the formation of the bromide anion and an organic radical occurs. The latter reacts to form a binaphthalene intrinsically chiral dimer. This paper is respectfully dedicated to Professors Anny Jutand and Christian Amatore for their outstanding contribution in the field of electrochemical catalysis and electrosynthesis.

1-bromo-2-methylnaphthalene↗
DOE OSTI2025

Mixed quantum-classical methods for polaron spectral functions

In this work, using two distinct semiclassical approaches—namely, the mean-field Ehrenfest method and the mapping approach to surface hopping—we investigate the spectral function of a single charge interacting with phonons on a lattice. This quantity is relevant for the description of angle-resolved photoemission experiments. Focusing on the one-dimensional Holstein model, we compare the performance of these approaches across a range of coupling strengths and lattice sizes, exposing the relative strengths and weaknesses of each. We demonstrate that these approaches can be efficiently applied with reasonable accuracy to ab initio polaron models. Furthermore, our work provides a route to the calculation of spectral properties in realistic electron–phonon-coupled systems in a computationally inexpensive manner with encouraging accuracy.

Atomic and molecular spectra↗
DOE OSTI2023

Introducing the embedded random phase approximation: H 2 dissociative adsorption on Cu(111) as an exemplar

The random phase approximation (RPA) as a means of treating electron correlation recently has been shown to outperform standard density functional theory (DFT) approximations in a variety of cases. However, the computational cost of the RPA is substantially more than DFT, especially when aiming to study extended surfaces. Properly accounting for sufficient surface ensemble size, Brillouin zone sampling, and vacuum separation of periodic images in standard periodic-planewave-based DFT code raises the cost to achieve converged results. Here, we show that sub-system embedding schemes enable use of the RPA for modeling heterogeneous reactions at reduced computational cost. Further, we explore two different embedded RPA (emb-RPA) approaches, periodic emb-RPA and cluster emb-RPA. We use the (experimentally and theoretically) well-studied H 2 dissociative adsorption on Cu(111) as our exemplar, and first perform full periodic RPA calculations as a benchmark. The full RPA results match well the semi-empirical barrier fit to experimental observables and others derived from high-level computations, e.g., from recent embedded n-electron valence second order perturbation theory [Zhao et al., J. Chem. Theory Comput. 16(11), 7078–7088 (2020)] and quantum Monte Carlo [Doblhoff-Dier et al., J. Chem. Theory Comput. 13(7), 3208–3219 (2017)] simulations. Among the two emb-RPA approaches tested, the cluster emb-RPA accurately reproduces the energy profile (maximum error of 50 meV along the reaction pathway) while reducing the computational cost by approximately two orders of magnitude. We therefore expect that the embedded cluster approach will enable wider RPA implementation in heterogeneous catalysis.

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

Embedded random phase approximation for magnetic systems: H 2 dissociative adsorption on Fe(110)

The random phase approximation (RPA), a method for treating electron correlation, has been shown to be superior to standard density functional theory (DFT) approximations in numerous cases. However, the RPA’s computational cost is substantially higher than that of DFT, particularly restricting its application to extended surfaces. The recently introduced embedded RPA (emb-RPA) approach [Wei et al., J. Chem. Phys. 159(19), 194108 (2023)] reduces this computational cost by approximately two orders of magnitude. While previous applications of emb-RPA focused on non-spin-polarized systems, here we extend the approach to ferromagnetic ones. Unlike other embedded correlated wavefunction methods, such as embedded complete active space self-consistent field theory, emb-RPA is advantageous for spin-polarized systems because the RPA is compatible with unrestricted DFT solutions, which are eigenfunctions of the spin angular momentum operator S z but not the total spin-squared operator S 2 . By applying emb-RPA with specific magnetization constraints, we achieved a speedup of two to three orders of magnitude (one order when accounting for the one-time embedding potential optimization cost) with only small errors (∼50 meV) compared to full periodic RPA. Moreover, emb-RPA significantly reduces the over-binding errors of DFT approximations. In conclusion, we anticipate that the acceleration enabled by the spin-polarized emb-RPA approach will broaden the applicability of RPA to magnetic materials.

Density functional theory↗
DOE OSTI2021

Broadband 2DES detection of vibrational coherence in the S x state of canthaxanthin

The nonadiabatic mechanism that mediates nonradiative decay of the bright S 2 state to the dark S 1 state of carotenoids involves population of a bridging intermediate state, S x , in several examples. The nature of S x remains to be determined definitively, but it has been recently suggested that S x corresponds to conformationally distorted molecules evolving along out-of-plane coordinates of the isoprenoid backbone near a low barrier between planar and distorted conformations on the S 2 potential surface. Here, the electronic and vibrational dynamics accompanying the formation of S x in toluene solutions of the ketocarotenoid canthaxanthin (CAN) are characterized with broadband two-dimensional electronic spectroscopy (2DES) with 7.8 fs excitation pulses and detection of the linear polarization components of the third-order nonlinear optical signal. A stimulated-emission cross peak in the 2DES spectrum accompanies the formation of S x in <20 fs following excitation of the main absorption band. S x is prepared instantaneously, however, with excitation of hot-band transitions associated with distorted conformations of CAN’s isoprenoid backbone in the low frequency onset of the main absorption band. Vibrational coherence oscillation maps and modulated anisotropy transients show that S x undergoes displacements from the Franck–Condon S 2 state along out-of-plane coordinates as it passes to the S 1 state. The results are consistent with the conclusion that CAN’s carbonyl-substituted β-ionone rings impart an intramolecular charge-transfer character that frictionally slows the passage from S x to S 1 compared to carotenoids lacking carbonyl substitution. Despite the longer lifetime, the S 1 state of CAN is formed with retention of vibrational coherence after passing through a conical intersection seam with the S x state.

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

PANNA: Properties from Artificial Neural Network Architectures

We report prediction of material properties from first principles is often a computationally expensive task. Recently, artificial neural networks and other machine learning approaches have been successfully employed to obtain accurate models at a low computational cost by leveraging existing example data. Here, we present a software package “Properties from Artificial Neural Network Architectures” (PANNA) that provides a comprehensive toolkit for creating neural network models for atomistic systems following the Behler–Parrinello topology. Besides the core routines for neural network training, it includes data parser, descriptor builder for Behler–Parrinello class of symmetry functions and force-field generator suitable for integration within molecular dynamics packages. PANNA offers a variety of activation and cost functions, regularization methods, as well as the possibility of using fully-connected networks with custom size for each atomic species. PANNA benefits from the optimization and hardware-flexibility of the underlying TensorFlow engine which allows it to be used on multiple CPU/GPU/TPU systems, making it possible to develop and optimize neural network models based on large datasets.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Mid-century climate change impacts on tornado-producing tropical cyclones

Tornadoes are a co-occurring extreme that can be produced by landfalling tropical cyclones (TCs). These tornadoes can exacerbate the loss of life and property damage caused by the TC from which they were spawned. It is uncertain how the severe weather environments of landfalling TCs may change in a future climate and how this could impact tornado activity from TCs. In this study, we investigated four TCs that made landfall in the U.S. and produced large tornado outbreaks. We performed four-member ensembles of convective-allowing (4-km resolution) regional climate model simulations representing each TC in the historical climate and a mid-twenty-first century future climate. To identify potentially tornadic storms, or TC-tornado (TCT) surrogates, we used thresholds for three-hourly maximum updraft helicity and radar reflectivity, as tornadoes are not resolved in the model. We found that the ensemble-mean number of TCT-surrogates increased substantially (56–299%) in the future, supported by increases in most-unstable convective available potential energy, surface-to-700-hPa bulk wind shear, and 0–1-km storm-relative helicity in the tornado-producing region of the TCs. On the other hand, future changes in most-unstable convective inhibition had minimal influence on future TCT-surrogates. This provides robust evidence that tornado activity from TCs may increase in the future. Furthermore, TCT-surrogate frequency between 00Z and 09Z increased for three of the four cases, suggesting enhanced tornado activity at night, when people are asleep and more likely to miss warnings. All of these factors indicate that TC-tornadoes may become more frequent and a greater hazard in the future, compounding impacts from future increases in TC winds and precipitation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Experimental and computational investigation of the bond energy of thorium dicarbonyl cation and theoretical elucidation of its isomerization mechanism to the thermodynamically most stable isomer, thorium oxide ketenylidene cation, OTh + CCO

Collision-induced dissociation (CID) of [Th,2C,2O] + with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). The only products observed are ThCO + and Th + by sequential loss of CO ligands. The experimental findings and theoretical calculations support that the structure of [Th,2C,2O] + is the bent homoleptic thorium dicarbonyl cation, Th + (CO) 2 , having quartet spin, which is both thermodynamically and kinetically stable enough in the gas phase to be observed in our GIBMS instrument. Analysis of the kinetic energy-dependent cross sections for this CID reaction yields the first experimental determination of the bond dissociation energy (BDE) of (CO)Th + –CO at 0 K as 1.05 ± 0.09 eV. A theoretical BDE calculated at the CCSD(T) level with cc-pVXZ (X = T and Q) basis sets and a complete basis set (CBS) extrapolation is in very good agreement with the experimental result. Although the doublet spin bent thorium oxide ketenylidene cation, OTh + CCO, is calculated to be the most thermodynamically stable structure, it is not observed in our experiment where [Th,2C,2O] + is formed by association of Th + and CO in a direct current discharge flow tube (DC/FT) ion source. Potential energy profiles of both quartet and doublet spin are constructed to elucidate the isomerization mechanism of Th + (CO) 2 to OTh + CCO. The failure to observe OTh + CCO is attributed to a barrier associated with C–C bond formation, which makes OTh + CCO kinetically inaccessible under our experimental conditions. Furthermore, chemical bonding patterns in low-lying states of linear and bent Th + (CO) 2 and OTh + CCO isomers are also investigated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗