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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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Analysis presented is an efficient technique to adjust previously calculated orthogonal polynomial coefficients for an odd number of equally spaced data points. The adjusting technique derivation is for a ninth order polynomial. It reduces computer time for smoothing functions.
This project worked towards developing predictive and practical methods for electron-ion dynamics, to model processes involved in solar energy conversion for eventual use in the design of photovoltaic devices. The methods centered on time-dependent density functional theory (TDDFT) for electrons, with coupling to ions described based on the recently developed exactfactorization approach.
Understanding the charging kinetics of electric double layers is of fundamental importance for the design and development of novel electrochemical devices such as supercapacitors and field-effect transistors. In this paper, we study the dynamic behavior of room-temperature ionic liquids using a classical time-dependent density functional theory that accounts for the molecular excluded volume effects, the electrostatic correlations, and the dispersion forces. While the conventional models predict a monotonic increase of the surface charge with time upon application of an electrode voltage, our results show that dispersion between ions results in a non-monotonic increase of the surface charge with the duration of charging. Finally and furthermore, we investigate the effects of van der Waals attraction between electrode/ionic-liquid interactions on the charging processes.
Pentaerythritol tetranitrate (PETN) is one of the most commonly used explosives for both military and mining applications. PETN is used in EBW (exploding bridge wire) and EFI (exploding foil initiator) detonator devices. Due the widespread usage of PETN, studies focusing on how the explosive changes with age, primarily its function in detonators has received particular interest. Aging studies have identified several factors that affect PETN detonator function over time, most notably the specific surface area of the explosive powder. Though small-scale studies have been performed on specific detonator systems with isolated batches of material, what is missing is a large statistically-significant study focusing on PETN aging characteristics - such as powder coarsening - and their influence on detonator performance. Herein we report the first large statistically viable PETN aging study focusing on four batches of PETN powder from the same stock of PETN using two stabilizers, polysaccharide and TriPEON. PETN was aged both as a free-flowing powder as well as in modified EBW RP-2 detonators, for one month at 75 °C. The PETN powder has been analyzed chemically using Fisher specific surface area analysis, SEM imaging and light scattering particle size analysis. Additionally the detonators were tested for performance through voltage-sweep threshold testing and function time measurements. Findings from the study indicate that aging at 75 °C for one month significantly changes the specific surface area and particle size of unstabilized PETN, leading to increases in detonator function time, but not detonator threshold values. Powders stabilized with TriPEON displayed less significant increases in function time, while powder stabilized with polysaccharide exhibited no aging effects, despite the high temperature aging.
Here, we present an improved energy decomposition analysis (EDA) scheme for understanding intermolecular interactions in delocalized excited states, especially in excimers. In the EDA procedure, excited states are treated with linear response theory such as configuration interaction singles (CIS) or time-dependent density functional theory (TDDFT), and absolutely localized molecular orbitals (ALMOs) are used to define the intermediate (frozen, excitonic coupling, and polarized) states. The intermolecular interaction energy is thereby separated into frozen, excitonic splitting, polarization, and charge transfer contributions. The excitonic splitting term describes the delocalization effect as two or more degenerate local excitations coupled with each other, which is often an important binding force in excimers. A maximum overlap state-tracking procedure is introduced to connect the initial fragment excitations to the constrained intermediate states and finally to the unconstrained delocalized states of the complex. The EDA scheme is applied to several excimer systems, including the He 2 * and Ne 2 * noble gas excimers, the doubly hydrogen-bonded 2-pyridone dimer, and the aromatic benzene and perylene excimers. We are able to gain some useful insights into the role each term is playing in the formation of these excimers, and the resulting method may also be useful for understanding a range of other complexes in excited states.
We focus on studying the opacity of iron, chromium, and nickel plasmas at conditions relevant to experiments carried out at Sandia National Laboratories. In this work, we calculate the photoabsorption cross sections and subsequent opacity for plasmas using linear-response time-dependent density functional theory (TD-DFT). Our results indicate that the physics of channel mixing accounted for in linear-response TD-DFT leads to an increase in the opacity in the bound-free quasicontinuum, where the Sandia experiments indicate that models underpredict iron opacity. However, the increase seen in our calculations is only in the range of 5%–10%. Further, we do not see any change in this trend for chromium and nickel. This behavior indicates that channel mixing effects do not explain the trends in opacity observed in the Sandia experiments.
The overarching goal of this project, which unfolded over a period of seventeen years, including two no-cost extensions in the last two years, was to extend and deepen our ability to use time-dependent density functional theory and related theoretical methods for the description of the transport of charge, spin, or energy in quantum electronic systems at the nanoscale. The output of our efforts is contained in 52 papers, listed below, which we have published since 2006. There have also been many presentations at international conferences, workshops, colloquia and seminars. This body of work has been carried out with the essential input of 8 postdoctoral students (who were supported by the grant) and several external senior collaborators and their postdocs.
Theoretical approach to design bright bio-imaging molecules is one of the most progressing ones. However, because of the system size and computational accuracy, the number of theoretical studies is limited to our knowledge. To overcome the difficulties, we developed a new method based on reference interaction site model self-consistent field explicitly including spatial electron density distribution and time-dependent density functional theory. We applied it to the calculation of indole and 5-cyanoindole at ground and excited states in gas and solution phases. The changes in the optimized geometries were clearly explained with resonance structures and the Stokes shift was correctly reproduced.
The number and properties of the neutrons and photons emitted in nuclear fission are directly related to the excitation energy of the fission fragments when they are formed at scission. Though not observable experimentally because of the extremely short timescales, the excitation energy of fission fragments can be predicted by microscopic theory based on time-dependent density functional theory (TDDFT). Initial results on the value of the total kinetic energy of fission reactions were very promising, but could not probe all possible fragmentations. Here, in this work, we perform large-scale TDDFT calculations in 240 Pu enabled by the development of a new TDDFT solver. We obtain TDDFT trajectories covering nearly all possible fragmentations. We find that the total kinetic energy is close to experimental values only for the most likely fission while it is severely underestimated at both small and large asymmetries. This conclusion seems rather independent of the parametrization of the energy functional, both in its particle-hole and particle-particle channels.
Liquid lithium is often used as a coating material in fusion reaction chambers, where it is under constant bombardment from high speed neutrons and protons. However, numerous fundamental questions are unanswered, for example whether a single proton impact can cause Li atom sputtering, and what is the electron excitation energy profile after a collision particularly for extremely high energy projectiles. Herein, we use a real-time dependent density functional method to study these questions for proton energies in the range of 30 eV to 1 MeV. The calculated stopping power agrees well with experiment, and it is found that the stopping power cannot be described by the single electron exciting spectrum based on the adiabatic eigen energies, and Li atom sputtering is not observed within our simulation time.
In nuclei with an odd nucleon number the nonvanishing spin number density is the source of a pseudomagnetic field, which favors the splitting of the nucleon Cooper pairs. Such a pseudomagnetic field is generated always in the dynamics of any nucleus, but its effects on Cooper pairs are significantly enhanced in the dynamic evolution of nuclei with an odd number of nucleons. We present for the first time a microscopic study of the induced fission of the odd neutron compound nuclei 239 U, 241,243 Pu, and the odd proton, odd neutron compound nucleus 238 Np, performed within the time-dependent density functional theory extended to superfluid fermion systems, without any simplifying assumptions, with controlled numerical approximations, and for a very large number of initial conditions. Because of the presence of the unpaired odd nucleon(s), the time-reversal symmetry of the fission compound nucleus is spontaneously broken, an aspect routinely neglected in the most advanced microscopic approaches of the past. The emerging fission fragment properties are quite similar to the properties of fission fragments of neighboring even-even nuclei. The time from saddle-to-scission is often significantly longer in odd-odd or odd-mass nuclei than for even-even nuclei, since systems with unpaired nucleons are easier to excite and the potential energy surfaces of these nuclei have more structure, often resembling a very complicated obstacle course, rather than a more direct evolution of the nuclear shape from the top of the outer fission barrier to the scission configuration. The Pauli blocking approximation, often invoked in the literature, expected to inhibit the fission of nuclei with unpaired nucleons, is surprisingly strongly violated during the fission dynamics.
The computation of the parton distribution functions (PDF) or distribution amplitudes (DA) of hadrons from first principles lattice QCD constitutes a central open problem in high energy nuclear physics. In this study, we present and evaluate the efficiency of several numerical methods, well established in the study of inverse problems, to reconstruct the full x-dependence of PDFs. Our starting point are the so called Ioffe time PDFs, which are accessible from Euclidean time simulations in conjunction with a matching procedure. Using realistic mock data tests, we find that the ill-posed incomplete Fourier transform underlying the reconstruction requires careful regularization, for which both the Bayesian approach as well as neural networks are efficient and flexible choices.
We present a full experimental and theoretical study of an interesting series of polycyclic aromatic hydrocarbons, the oligorylenes. The absorption spectra of perylene, terrylene and quaterrylene in neutral, cationic and anionic charge states are obtained by matrix-isolation spectroscopy in Ne. The experimental spectra are dominated by a bright state that red shifts with growing molecular size. Excitation energies and state symmetry assignments are supported by calculations using time dependent density functional theory methods. These calculations also provide new insight into the observed trends in oscillator strength and excitation energy for the bright states: the oscillator strength per unit mass of carbon increases along the series.
A series of 1,3,5-triazines were synthesized and their UV absorption properties were tested. The computational chemistry methods were used to construct quantitative structure-property relationship (QSPR), which was used to computer aided design of new 1,3,5-triazines ultraviolet rays absorber compounds. The experimental UV absorption data are in good agreement with those predicted data using the Time-dependent density functional theory (TD-DFT) [B3LYP/6–311 + G(d,p)]. A suitable forecasting model (R > 0.8, P < 0.0001) was revealed. Predictive three-dimensional quantitative structure-property relationship (3D-QSPR) model was established using multifit molecular alignment rule of Sybyl program, which conclusion is consistent with the TD-DFT calculation. The exceptional photostability mechanism of such ultraviolet rays absorber compounds was studied and confirmed as principally banked upon their ability to undergo excited-state deactivation via an ultrafast excited-state proton transfer (ESIPT). The intramolecular hydrogen bond (IMHB) of 1,3,5-triazines compounds is the basis for the excited state proton transfer, which was explored by IR spectroscopy, UV spectra, structural and energetic aspects of different conformers and frontier molecular orbitals analysis.
Photoinduced phase transitions can have complex and intriguing behaviors more than material ground-state dynamics. Understanding the underlying mechanism can help us to design new ways to manipulate the materials. A variety of mechanisms has been proposed to explain the photoinduced phase transitions of IrTe 2 , but a consensus has yet to be reached. Here, we study the photo-induced phase transitions of IrTe 2 by performing the real-time time-dependent density functional theory (rt-TDDFT) simulations in combination with the occupation constrained DFT method. We reveal that the microscopic driving force for the photo-induced phase transitions arises from the tendency to lower the energy levels occupied by the excited carriers, through the increase or decrease of the associated atomic pair distances, depending on whether the newly occupied states are antibonding or bonding states, respectively. The geometric constraints between different bonds represented by the Poisson ratio can bring together different tendencies from different atomic pairs, thus forming a complex intriguing dynamic picture depending on the intensity of the excitation. Furthermore, we also find that phonons don't play a primary role, but can assist the phase transition. These findings imply that one can control the structural phase transitions by selectively exciting photocarriers into designated atomic states using appropriate photon sources.
With the help of newly developed X-ray free-electron laser (XFEL) sources, creating double core holes (DCHs) simultaneously at the same or different atomic sites in a molecule has now become possible. DCH X-ray emission is a new form of X-ray nonlinear spectroscopy that can be studied with a XFEL. Here in this paper, we computationally explore the metal K-edge valence-to-core (VtC) X-ray emission spectroscopy (XES) of metal/metal and metal/ligand DCH states in a series of transition metal complexes with time-dependent density functional theory. The simulated DCH VtC-XES signals are compared with conventional single core hole (SCH) XES signals. The energy shifts and intensity changes of the DCH emission lines with respect to the corresponding SCH-XES features are fingerprints of the coupling between the second core hole and the occupied orbitals around the DCHs that contain important chemical bonding information of the complex. The difference between delocalized/localized core hole models on DCH VtC-XES is also briefly discussed. We theoretically demonstrate that DCH XES provides subtle information on the local electronic structure around metal centers in transition metal complexes beyond conventional linear XES. In conclusion, our predicted changes from calculations between SCH-XES and DCH-XES features should be detectable with modern XFEL sources.
Electronically excited states characterized by intramolecular charge transfer play an essential role in many biological processes and optical devices. The ability to make quantitative ab initio predictions of the relative energetics involved is a challenging yet desirable goal, especially for large molecules in solution. In this work, we present a data set of 61 experimental measurements of absorption and emission processes, both in the gas phase and in solvents representing a broad range of polarities, which involve intramolecular charge transfer mediated by a nonzero, "twisted" dihedral angle between one or more donor and acceptor subunits. Among a variety of density functionals investigated within the framework of linear-response theory, the "optimally tuned" LRC-ωPBE functional, which utilizes a system-specific yet nonempirical procedure to specify the range-separation parameter, emerges as the preferred choice. For the entire set of excitation energies, involving changes in dipole moment ranging from 4 to >20 Debye, the mean signed and absolute errors are 0.02 and 0.18 eV, respectively (compared, e.g., to -0.30 and 0.30 for PBE0, 0.44 and 0.47 for LRC-ωPBEh, 0.83 and 0.83 for ωB97X-V). We analyze the performance of polarizable continuum solvation models available in Q-Chem that partition the solvent response into fast and slow time scales, and clear trends emerge when measurements corresponding to the four small 4-(dimethylamino)benzonitrile (DMABN)-like molecules and a charged species are excluded. We make the case that the large errors found only for small molecules in the gas phase and weak solvents cannot be expected to improve via the optimal tuning procedure, which enforces a condition that is exact only in the well-separated donor-acceptor limit, and present empirical evidence implicating the outsized importance for small donor-acceptor systems of relaxation effects that cannot be accounted for by the linear-response time-dependent density functional theory within the adiabatic approximation. Finally, we demonstrate the utility of the optimally tuned density functional approach by targeting the charge-transfer states of a large biomimetic model system for light-harvesting structures in Photosystem II.
The spectral relations for the four-time fermionic Green's functions are derived in the most general case. The terms which correspond to the zero-frequency anomalies, known before only for the bosonic Green's functions, are separated and their connection with the second cumulants of the Boltzmann distribution function is elucidated. Furthermore, the high-frequency expansions of the four-time fermionic Green's functions are provided for different directions in the frequency space.