Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ELECTRON SPECTRA”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Electronic spectra from TDDFT and machine learning in chemical space

Due to its favorable computational efficiency, time-dependent (TD) density functional theory (DFT) enables the prediction of electronic spectra in a high-throughput manner across chemical space. Its predictions, however, can be quite inaccurate. We resolve this issue with machine learning models trained on deviations of reference second-order approximate coupled-cluster (CC2) singles and doubles spectra from TDDFT counterparts, or even from DFT gap. We applied this approach to low-lying singlet-singlet vertical electronic spectra of over 20 000 synthetically feasible small organic molecules with up to eight CONF atoms. The prediction errors decay monotonously as a function of training set size. For a training set of 10 000 molecules, CC2 excitation energies can be reproduced to within ±0.1 eV for the remaining molecules. Analysis of our spectral database via chromophore counting suggests that even higher accuracies can be achieved. Based on the evidence collected, we discuss open challenges associated with data-driven modeling of high-lying spectra and transition intensities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes

Coherence oscillations measured in two-dimensional (2D) electronic spectra of pigment-protein complexes may have electronic, vibrational, or mixed-character vibronic origins, which depend on the degree of electronic-vibrational mixing. Oscillations from intrapigment vibrations can obscure the inter-site coherence lifetime of interest in elucidating the mechanisms of energy transfer in photosynthetic light-harvesting. Huang-Rhys factors (S) for low-frequency vibrations in Chlorophyll and Bacteriochlorophyll are quite small (S ≤ 0.05), so it is often assumed that these vibrations influence neither 2D spectra nor inter-site coherence dynamics. In this work, we explore the influence of S within this range on the oscillatory signatures in simulated 2D spectra of a pigment heterodimer. To visualize the inter-site coherence dynamics underlying the 2D spectra, we introduce a formalism which we call the “site-probe response.” By comparing the calculated 2D spectra with the site-probe response, we show that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-resonance vibrations (S = 0.05) give rise to long-lived, purely vibrational coherences at 77 K. We moreover calculate the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence. At 77 K, greater long-lived inter-site coherence and entanglement appear with increasing S. This dependence all but vanishes at physiological temperature, as environmentally induced fluctuations destroy the vibronic mixing.

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

Extracting the Frequency-Dependent Dynamic Stokes Shift from Two-Dimensional Electronic Spectra with Prominent Vibrational Coherences

The dynamic Stokes shift is a common means for characterizing ultrafast solvation dynamics of electronically excited states. Here we extract the excitation frequency-dependent dynamic Stokes shift from two-dimensional electronic spectra (2DES) of cresyl violet, a molecule with a well-defined vibronic progression. The extracted dynamic Stokes shift function, S(t), exhibits oscillatory behavior, and the oscillatory components are assigned to intramolecular vibrational modes through DFT and TD-DFT calculations. Here, the well-characterized oscillations are incorporated into the fitting procedure of S(t). The excitation frequency dependence of the ultrafast response is examined through the analysis of S(t) obtained from slices taken at different excitation frequencies of the 2DES spectra. The extracted ultrafast timescales range from 36 to 98 fs, and we interpret the frequency dependence of the timescales in the context of other dynamic processes that also lead to lineshape changes in the 2DES spectrum, such as vibrational energy relaxation and spectral diffusion. Through comparison of the extracted timescales, we find that the fastest timescales are extracted over a range of excitation frequencies, where contributions from vibrational relaxation and spectral diffusion can be minimized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Influences of Quantum Mechanically Mixed Electronic and Vibrational Pigment States in 2D Electronic Spectra of Photosynthetic Systems: Strong Electronic Coupling Cases

In 2D electronic spectroscopy studies, long-lived quantum beats have recently been observed in photosynthetic systems, and several theoretical studies have suggested that the beats are produced by quantum mechanically mixed electronic and vibrational states. Concerning the electronic-vibrational quantum mixtures, the impact of protein-induced fluctuations was examined by calculating the 2D electronic spectra of a weakly coupled dimer with the Franck-Condon active vibrational modes in the resonant condition. This analysis demonstrated that quantum mixtures of the vibronic resonance are rather robust under the influence of the fluctuations at cryogenic temperatures, whereas the mixtures are eradicated by the fluctuations at physiological temperatures. However, this conclusion cannot be generalized because the magnitude of the coupling inducing the quantum mixtures is proportional to the inter-pigment electronic coupling. In this paper, we explore the impact of the fluctuations on electronic-vibrational quantum mixtures in a strongly coupled dimer with an off-resonant vibrational mode. Toward this end, we calculate energy transfer dynamics and 2D electronic spectra of a model dimer that corresponds to the most strongly coupled bacteriochlorophyll molecules in the Fenna-Matthews-Olson complex in a numerically accurate manner. The quantum mixtures are found to be robust under the exposure of protein-induced fluctuations at cryogenic temperatures, irrespective of the resonance. At 300 K, however, the quantum mixing is disturbed more strongly by the fluctuations, and therefore, the beats in the 2D spectra become obscure even in a strongly coupled dimer with a resonant vibrational mode. Further, the overall behaviors of the energy transfer dynamics are demonstrated to be dominated by the environment and coupling between the 0 0 vibronic transitions as long as the Huang-Rhys factor of the vibrational mode is small. Finally, the electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics despite contributing to the enhancement of long-lived quantum beating in the 2D spectra.

2D electronic spectra↗
DOE OSTI2023

An accurate and efficient Ehrenfest dynamics approach for calculating linear and nonlinear electronic spectra

Linear and nonlinear electronic spectra provide an important tool to probe the absorption and transfer of electronic energy. Here, we introduce a pure state Ehrenfest approach to obtain accurate linear and nonlinear spectra that is applicable to systems with large numbers of excited states and complex chemical environments. We achieve this by representing the initial conditions as sums of pure states and unfolding multi-time correlation functions into the Schrödinger picture. By doing this, we show that one can obtain significant improvements in accuracy over the previously used projected Ehrenfest approach and that these benefits are particularly pronounced in cases where the initial condition is a coherence between excited states. While such initial conditions do not arise when calculating linear electronic spectra, they play a vital role in capturing multidimensional spectroscopies. We demonstrate the performance of our method by showing that it is able to quantitatively capture the exact linear, 2D electronic spectroscopy, and pump–probe spectra for a Frenkel exciton model in slow bath regimes and is even able to reproduce the main spectral features in fast bath regimes.

Chemistry↗
DOE OSTI2015

Impact of environmentally induced fluctuations on quantum mechanically mixed electronic and vibrational pigment states in photosynthetic energy transfer and 2D electronic spectra

Recently, nuclear vibrational contribution signatures in two-dimensional (2D) electronic spectroscopy have attracted considerable interest, in particular as regards interpretation of the oscillatory transients observed in light-harvesting complexes. These transients have dephasing times that persist for much longer than theoretically predicted electronic coherence lifetime. As a plausible explanation for this long-lived spectral beating in 2D electronic spectra, quantum-mechanically mixed electronic and vibrational states (vibronic excitons) were proposed by Christensson et al. [J. Phys. Chem. B 116, 7449 (2012)] and have since been explored. In this work, we address a dimer which produces little beating of electronic origin in the absence of vibronic contributions, and examine the impact of protein-induced fluctuations upon electronic-vibrational quantum mixtures by calculating the electronic energy transfer dynamics and 2D electronic spectra in a numerically accurate manner. It is found that, at cryogenic temperatures, the electronic-vibrational quantum mixtures are rather robust, even under the influence of the fluctuations and despite the small Huang-Rhys factors of the Franck-Condon active vibrational modes. This results in long-lasting beating behavior of vibrational origin in the 2D electronic spectra. At physiological temperatures, however, the fluctuations eradicate the mixing, and hence, the beating in the 2D spectra disappears. Further, it is demonstrated that such electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics, despite contributing to the enhancement of long-lived quantum beating in 2D electronic spectra, contrary to speculations in recent publications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

On the analysis of photo-electron spectra

We analyze Photo-Electron Spectra (PES) for a variety of excitation mechanisms from a simple mono-frequency laser pulse to involved combination of pulses as used, e.g., in attosecond experiments. In the case of simple pulses, the peaks in PES reflect the occupied single-particle levels in combination with the given laser frequency. This usual, simple rule may badly fail in the case of excitation pulses with mixed frequencies and if resonant modes of the system are significantly excited. We thus develop an extension of the usual rule to cover all possible excitation scenarios, including mixed frequencies in the attosecond regime. We find that the spectral distributions of dipole, monopole and quadrupole power for the given excitation taken together and properly shifted by the single-particle energies provide a pertinent picture of the PES in all situations. This leads to the derivation of a generalized relation allowing to understand photo-electron yields even in complex experimental setups.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1998

Radial Distribution of Electron Spectra from High-Energy Ions

The average track model describes the response of physical and biological systems using radial dose distribution as the key physical descriptor. We report on an extension of this model to describe the average distribution of electron spectra as a function of radial distance from an ion. We present calculations of these spectra for ions of identical linear energy transfer (LET), but dissimilar charge and velocity to evaluate the differences in electron spectra from these ions. To illustrate the usefulness of the radial electron spectra for describing effects that are not described by electron dose, we consider the evaluation of the indirect events in microdosimetric distributions for ions. We show that folding our average electron spectra model with experimentally determined frequency distributions for photons or electrons provides a good representation of radial event spectra from high-energy ions in 0.5-2 micrometer sites.

Cucinotta, Francis A.↗
DOE OSTI2015

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO{sub 2}

The electronic spectra of neutral NpO and NpO{sub 2} as well as of their mono- (NpO{sup +}, NpO{sub 2}{sup +}) and dications (NpO{sup 2+}, NpO{sub 2}{sup 2+}) were studied using multiconfigurational relativistic quantum chemical calculations at the complete active space self-consistent field/CASPT2 level of theory taking into account spin-orbit coupling. The active space included 16 orbitals: all the 7s, 6d, and 5f orbitals of neptunium together with selected orbitals of oxygen. The vertical excitation energies on the ground state geometries have been computed up to ca. 35 000 cm{sup −1}. The gas-phase electronic spectra were evaluated on the basis of the computed Einstein coefficients at 298 K and 3000 K. The computed vertical transition energies show good agreement with previous condensed-phase results on NpO{sub 2}{sup +} and NpO{sub 2}{sup 2+}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Electron Bremsstrahlung Hard X-Ray Spectra, Electron Distributions and Energetics in the 2002 July 23 Solar Flare

We present and analyze the first high-resolution hard X-ray spectra from a solar flare observed in both X-ray/gamma-ray continuum and gamma-ray lines. The 2002 July 23 flare was observed by the Ramaty High Energy Solar Spectroscopic Imager (RHESSI). The spatially integrated photon flux spectra are well fitted between 10 and 300 keV by the combination of an isothermal component and a double power law. The flare plasma temperature peaks at 40 MK around the time of peak hard X-ray emission and remains above 20 MK 37 min later. We derive the evolution of the nonthermal mean electron flux distribution by directly fitting the RHESSI X-ray spectra with the thin-target bremsstrahlung from a double power-law electron distribution with a low-energy cutoff. We also derive the evolution of the electron flux distribution on the assumption that the emission is thick-target bremsstrahlung. We find that the injected nonthermal electrons are well described throughout the flare by this double power-law distribution with a low-energy cutoff that is typically between 20 - 40 keV. Using our thick-target results, we compare the energy contained in the nonthermal electrons with the energy content of the thermal flare plasma observed by RHESSI and GOES. We find that the minimum total energy deposited into the flare plasma by nonthermal electrons, 2.6 x 10(exp 31) erg, is on the order of and possibly less than the energy in the thermal plasma. However, these fits do not rule out the possibility that the energy in nonthermal electrons exceeds the energy in the thermal plasma. This work was supported in part by the RHESSI Project and the NASA Sun-Earth Connection program.

Holman, G. D.↗
NASA NTRS2003

Electron Bremsstrahlung Hard X-Ray Spectra, Electron Distributions and Energetics in the 2002 July 23 Solar Flare

We present and analyze the first high-resolution hard X-ray spectra from a solar flare observed in both X-ray/gamma-ray continuum and gamma-ray lines. The 2002 July 23 flare was observed by the Ramaty High Energy Solar Spectroscopic Imager (RHESSI). The spatially integrated photon flux spectra are well fitted between 10 and 300 keV by the combination of an isothermal component and a double power law. The flare plasma temperature peaks at 40 MK around the time of peak hard X-ray emission and remains above 20 MK 37 min later. We derive the evolution of the nonthermal mean electron flux distribution by directly fitting the RHESSI X-ray spectra with the thin-target bremsstrahlung from a double power-law electron distribution with a low-energy cutoff. We also derive the evolution of the electron flux distribution on the assumption that the emission is thick-target bremsstrahlung. We find that the injected nonthermal electrons are well described throughout the flare by this double power-law distribution with a low-energy cutoff that is typically between 20-40 keV. Using our thick-target results, we compare the energy contained in the nonthermal electrons with the energy content of the thermal flare plasma observed by RHESSI and GOES. We find that the minimum total energy deposited into the flare plasma by nonthermal electrons, 2.6 x 10(exp 31)erg, is on the order of and possibly less than the energy in the thermal plasma. However, these fits do not rule out the possibility that the energy in nonthermal electrons exceeds the energy in the thermal plasma.

Holman, Gordon D.↗
DOE OSTI2016

Ultra-fast computation of electronic spectra for large systems by tight-binding based simplified Tamm-Dancoff approximation (sTDA-xTB)

The computational bottleneck of the extremely fast simplified Tamm-Dancoff approximated (sTDA) time-dependent density functional theory procedure [S. Grimme, J. Chem. Phys. 138, 244104 (2013)] for the computation of electronic spectra for large systems is the determination of the ground state Kohn-Sham orbitals and eigenvalues. This limits such treatments to single structures with a few hundred atoms and hence, e.g., sampling along molecular dynamics trajectories for flexible systems or the calculation of chromophore aggregates is often not possible. The aim of this work is to solve this problem by a specifically designed semi-empirical tight binding (TB) procedure similar to the well established self-consistent-charge density functional TB scheme. The new special purpose method provides orbitals and orbital energies of hybrid density functional character for a subsequent and basically unmodified sTDA procedure. Compared to many previous semi-empirical excited state methods, an advantage of the ansatz is that a general eigenvalue problem in a non-orthogonal, extended atomic orbital basis is solved and therefore correct occupied/virtual orbital energy splittings as well as Rydberg levels are obtained. A key idea for the success of the new model is that the determination of atomic charges (describing an effective electron-electron interaction) and the one-particle spectrum is decoupled and treated by two differently parametrized Hamiltonians/basis sets. The three-diagonalization-step composite procedure can routinely compute broad range electronic spectra (0-8 eV) within minutes of computation time for systems composed of 500-1000 atoms with an accuracy typical of standard time-dependent density functional theory (0.3-0.5 eV average error). An easily extendable parametrization based on coupled-cluster and density functional computed reference data for the elements H–Zn including transition metals is described. The accuracy of the method termed sTDA-xTB is first benchmarked for vertical excitation energies of open- and closed-shell systems in comparison to other semi-empirical methods and applied to exemplary problems in electronic spectroscopy. As side products of the development, a robust and efficient valence electron TB method for the accurate determination of atomic charges as well as a more accurate calculation scheme of dipole rotatory strengths within the Tamm-Dancoff approximation is proposed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Complex time dependent wave packet technique for thermal equilibrium systems - Electronic spectra

A time dependent wave packet method is presented for the rapid calculation of the properties of systems in thermal equilibrium and is applied, as an illustration, to electronic spectra. The thawed Gaussian approximation to quantum wave packet dynamics combined with evaluation of the density matrix operator by imaginary time propagation is shown to give exact electronic spectra for harmonic potentials and excellent results for both a Morse potential and for the band contours of the three transitions of the visible electronic absorption spectrum of the iodine molecule. The method, in principle, can be extended to many atoms (e.g., condensed phases) and to other properties (e.g., infrared and Raman spectra and thermodynamic variables).

Reimers, J. R.↗
DOE OSTI2017

Gas-phase Electronic Spectra of Coronene and Corannulene Cations

Gas-phase electronic spectra of the coronene (C{sub 24}H{sub 12}{sup +}) and corannulene (C{sub 20}H{sub 10}{sup +}) cations complexed with helium have been recorded in a quadrupole ion trap at 5 K by photodissociation. The electronic spectrum of C{sub 20}H{sub 10}{sup +} with two helium atoms was also measured to estimate the perturbation. This method is sufficient for an astronomical comparison because the shift due to the weakly bound helium is on the order of 0.2 Å. C{sub 24}H{sub 12}{sup +}--He has the origin band of the A{sup 2}E{sub 1g}←X{sup 2}E{sub 2u} transition at 9438.3 Å and that to a much higher state D{sub 3}←X{sup 2}E{sub 2u} at 4570 Å. The corannulene cation is subject to a Jahn–Teller distortion in the electronic ground state, leading to the 3{sup 2}A{sup ′}←X{sup 2}A{sup ′′} and 3{sup 2}A{sup ′′}←X{sup 2}A{sup ′} transitions with origin band maxima when complexed with helium at 5996.1 and 5882.6 Å. These absorptions lie in a region where there is a congestion of diffuse interstellar bands (DIBs). However, the recorded features have no match with astronomical observations, removing coronene and corannulene cations and probably other aromatic hydrocarbons of this size as possible carriers of the DIBs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

COLLISIONAL RELAXATION OF ELECTRONS IN A WARM PLASMA AND ACCELERATED NONTHERMAL ELECTRON SPECTRA IN SOLAR FLARES

Extending previous studies of nonthermal electron transport in solar flares, which include the effects of collisional energy diffusion and thermalization of fast electrons, we present an analytic method to infer more accurate estimates of the accelerated electron spectrum in solar flares from observations of the hard X-ray spectrum. Unlike for the standard cold-target model, the spatial characteristics of the flaring region, especially the necessity to consider a finite volume of hot plasma in the source, need to be taken into account in order to correctly obtain the injected electron spectrum from the source-integrated electron flux spectrum (a quantity straightforwardly obtained from hard X-ray observations). We show that the effect of electron thermalization can be significant enough to nullify the need to introduce an ad hoc low-energy cutoff to the injected electron spectrum in order to keep the injected power in non-thermal electrons at a reasonable value. Rather, the suppression of the inferred low-energy end of the injected spectrum compared to that deduced from a cold-target analysis allows the inference from hard X-ray observations of a more realistic energy in injected non-thermal electrons in solar flares.

79 ASTRONOMY AND ASTROPHYSICS↗