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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
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 OSTI2025

Fast methods for multisite charge transfer. Processes II. Analytic nuclear gradients and nonadiabatic dynamics for cCASSCF(1,n) and cCASSCF(2n-1,n) wavefunctions

In this work we derive and implement analytic nuclear gradients and derivative couplings for a constrained complete active space self-consistent field with a small active space designed to model electron or hole transfer. Using a Lagrangian formalism, we are able to differentiate both the CASSCF energy and the constraint (which is required for smooth surfaces over a wide range of parameter space), and the resulting efficient algorithm can be immediately applied to nonadiabatic dynamics simulations of charge transfer processes. Here, we run initial surface-hopping simulations of a proton coupled electron transfer event for a phenoxyl–phenol system.

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

Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory

Herein, we present the first implementation of multiconfiguration pair-density functional theory (MC-PDFT) ab initio molecular dynamics. MC-PDFT is a multireference electronic structure method that in many cases has a similar accuracy (or even better accuracy) the complete active space second-order perturbation theory (CASPT2) at a significantly lower computational cost. In this study, we introduced MC-PDFT analytical gradients into the SHARC molecular dynamics program for ab initio, nonadiabatic molecular dynamics simulations. We verify our implementation by examining the intersystem crossing dynamics of thioformaldehyde, and we observe excellent agreement with recent CASPT2 and experimental findings. Moreover, with MC-PDFT, we could perform dynamics simulations with the 12 electron in 10 orbitals active space that was computationally too expensive for direct dynamics with CASPT2.

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

Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Abstract Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited‐state trajectories of a diplatinum complex featuring photo‐activated metal–metal σ ‐bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide‐angle X‐ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited‐state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non‐equilibrium processes along excited‐state trajectories involving multiple excited‐state PESs.

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

Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Abstract Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited‐state trajectories of a diplatinum complex featuring photo‐activated metal–metal σ ‐bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide‐angle X‐ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited‐state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non‐equilibrium processes along excited‐state trajectories involving multiple excited‐state PESs.

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

Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics

Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, in this paper, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au 20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au 20 beyond the Born–Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au 20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7 ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au 20 cluster. Furthermore, our simulations show that the lifetime of the phonon-induced plasmon dephasing process is ~10.4 fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.

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

Sub-100-fs energy transfer in coenzyme NADH is a coherent process assisted by a charge-transfer state

Excitation energy transfer (EET) is a key photoinduced process in biological chromophoric assemblies. Here we investigate the factors which can drive EET into efficient ultrafast sub-ps regimes. We demonstrate how a coherent transport of electronic population could facilitate this in water solvated NADH coenzyme and uncover the role of an intermediate dark charge-transfer state. High temporal resolution ultrafast optical spectroscopy gives a 54 ± 11 fs time constant for the EET process. Nonadiabatic quantum dynamical simulations computed through the time-evolution of multidimensional wavepackets suggest that the population transfer is mediated by photoexcited molecular vibrations due to strong coupling between the electronic states. The polar aqueous solvent environment leads to the active participation of a dark charge transfer state, accelerating the vibronically coherent EET process in favorably stacked conformers and solvent cavities. Our work demonstrates how the interplay of structural and environmental factors leads to diverse pathways for the EET process in flexible heterodimers and provides general insights relevant for coherent EET processes in stacked multichromophoric aggregates like DNA strands.

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

Conical Intersection Passages of Molecules Probed by X-ray Diffraction and Stimulated Raman Spectroscopy

Conical intersections (CoIns) play an important role in ultrafast relaxation channels. Their monitoring remains a formidable experimental challenge. We theoretically compare the probing of the S 2 → S 1 CoIn passage in 4-thiouracil by monitoring its vibronic coherences, using off-resonant X-ray-stimulated Raman spectroscopy (TRUECARS) and time resolved X-ray diffraction (TRXD). The quantum nuclear wavepacket (WP) dynamics provides an accurate picture of the photoinduced dynamics. Upon photoexcitation, the WP oscillates among the Franck–Condon point, the S2 minimum, and the CoIn with a 70 fs period. A vibronic coherence first emerges at 20 fs and can be observed until the S 2 state is fully depopulated. The distribution of the vibronic frequencies involved in the coherence is recorded by the TRUECARS spectrogram. Here, the TRXD signal provides spatial images of electron densities associated with the CoIn. In combination, the two signals provide a complementary picture of the nonadiabatic passage, which helps in the study of the underlying photophysics in thiobases.

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

Energy conservation in real-time nuclear–electronic orbital Ehrenfest dynamics

Real-time nuclear–electronic orbital Ehrenfest (RT-NEO-Ehrenfest) dynamics methods provide a first-principles approach for describing nonadiabatic molecular processes with nuclear quantum effects. For an efficient description of proton transfer within RT-NEO-Ehrenfest dynamics, the basis function center associated with the quantum proton can be allowed to move classically. Here, this traveling proton basis (TPB) approach effectively captures proton quantum dynamics, although its energy conservation behavior is not yet fully satisfactory. Two recently proposed TPB approaches, in principle, conserve the extended energy, which includes both the system energy and the kinetic energy associated with the proton basis function center. Herein, a thermostatted TPB approach is proposed to improve the conservation of the system energy, excluding the kinetic energy associated with the proton basis function center. In this approach, the quantum proton dynamics are modulated by dynamically rescaling the proton momentum operator to maintain the system energy conservation. With the excited-state intramolecular proton transfer of o-hydroxybenzaldehyde as an example, this approach is shown to significantly improve the system energy conservation while preserving the accuracy of the quantum proton dynamics as achieved in the original TPB approach.

Ehrenfest dynamics↗
NASA NTRS1969

Nonadiabatic translations in polyatomic molecules

Matrix elements of nonadiabatic perturbation emphasized in semiempirical theory for evaluating polyatomic molecules radiationless rate constants in terms of electronic-vibrational state

Young, J. H.↗
DOE OSTI2021

High-fidelity first principles nonadiabaticity: diabatization, analytic representation of global diabatic potential energy matrices, and quantum dynamics

We report nonadiabatic dynamics, which goes beyond the Born–Oppenheimer approximation, has increasingly been shown to play an important role in chemical processes, particularly those involving electronically excited states. Understanding multistate dynamics requires rigorous quantum characterization of both electronic and nuclear motion. However, such first principles treatments of multi-dimensional systems have so far been rather limited due to the lack of accurate coupled potential energy surfaces and difficulties associated with quantum dynamics. In this Perspective, we review recent advances in developing high-fidelity analytical diabatic potential energy matrices for quantum dynamical investigations of polyatomic uni- and bi-molecular nonadiabatic processes, by machine learning of high-level ab initio data. Special attention is paid to methods of diabatization, high fidelity construction of multi-state coupled potential energy surfaces and property surfaces, as well as quantum mechanical characterization of nonadiabatic nuclear dynamics. To illustrate the tremendous progress made by these new developments, several examples are discussed, in which direct comparison with quantum state resolved measurements led to either confirmation of the observation or sometimes reinterpretation of the experimental data. The insights gained in these prototypical systems greatly advance our understanding of nonadiabatic dynamics in chemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2022

The Atmospheric Response to High Nonthermal Electron-beam Fluxes in Solar Flares. II. Hydrogen-broadening Predictions for Solar Flare Observations with the Daniel K. Inouye Solar Telescope

Redshifted components of chromospheric emission lines in the hard X-ray impulsive phase of solar flares have recently been studied through their 30 s evolution with the high resolution of the Interface Region Imaging Spectrograph. Radiative-hydrodynamic flare models show that these redshifts are generally reproduced by electron-beam-generated chromospheric condensations. The models produce large ambient electron densities, and the pressure broadening of the hydrogen Balmer series should be readily detected in observations. To accurately interpret the upcoming spectral data of flares with the DKIST, we incorporate nonideal, nonadiabatic line-broadening profiles of hydrogen into the RADYN code. These improvements allow time-dependent predictions for the extreme Balmer line wing enhancements in solar flares. We study two chromospheric condensation models, which cover a range of electron-beam fluxes (1 − 5 × 10^(11) erg s^(−1) cm^(−2)) and ambient electron densities (1 − 60 × 10^(13) cm^(−3)) in the flare chromosphere. Both models produce broadening and redshift variations within 10 s of the onset of beam heating. In the chromospheric condensations, there is enhanced spectral broadening due to large optical depths at Hα, Hβ, and Hγ, while the much lower optical depth of the Balmer series H12−H16 provides a translucent window into the smaller electron densities in the beam-heated layers below the condensation. The wavelength ranges of typical DKIST/ViSP spectra of solar flares will be sufficient to test the predictions of extreme hydrogen wing broadening and accurately constrain large densities in chromospheric condensations.

Adam F. Kowalski↗
DOE OSTI2020

Nonadiabatic molecular dynamics simulation of C2H22+ in a strong laser field*

We investigate the alignment dependence of the strong laser dissociation dynamics of molecule C 2 H 2 2 + in the frame of real-time and real-space time-dependent density function theory coupled with nonadiabatic quantum molecular dynamics (TDDFT-MD) simulation. This work is based on a recent experiment study “ultrafast electron diffraction imaging of bond breaking in di-ionized acetylene” [Wolter et al , Science 354 , 308–312 (2016)]. Our simulations are in excellent agreement with the experimental data and the analysis confirms that the alignment dependence of the proton dissociation dynamics comes from the electron response of the driving laser pulse. Our results validate the ability of the TDDFT-MD method to reveal the underlying mechanism of experimentally observed and control molecular dissociation dynamics.

Physics↗
DOE OSTI2023

Out-of-equilibrium Majorana zero modes in interacting Kitaev chains

Here, we employ a time-dependent real-space local density-of-states method to study the movement and fusion of Majorana zero modes in the one-dimensional interacting Kitaev model, based on the time evolution of many-body states. We analyze the dynamics and both fusion channels of Majoranas using time-dependent potentials, either creating walls or wells. For fast moving Majoranas, we unveil nonequilibrium signatures of the “strong-zero-mode” operator (quasiparity degeneracy in the full spectrum) and its breakdown in the presence of repulsive Coulomb interactions. Focusing on forming a full electron after fusion, we also discuss the upper and lower limits on the Majorana speed needed to reduce nonadiabatic effects and to avoid poisoning due to decoherence.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Nuclear–Electronic Orbital General Rate Theory: Predicting Hydrogen Kinetic Isotope Effects in the Deep Tunneling Regime

Hydrogen transfer is a critical component of many chemical and biological processes. The ratio of rate constants for hydrogen and deuterium transfer defines the H/D kinetic isotope effect (KIE), which is a powerful tool for elucidating hydrogen transfer mechanisms. Interpretation of experimental H/D KIEs relies on accurate and affordable computational methods. However, due to their light mass, hydrogen and deuterium can undergo tunneling, which is challenging to describe in multidimensional molecular systems. Herein, we introduce the nuclear–electronic orbital general rate theory (NEO-GRT), which enables the efficient prediction of H/D KIEs based on full-dimensional molecular quantum chemistry calculations. The NEO-GRT approach describes the hydrogen transfer rate constant with a general expression that spans the vibrationally adiabatic and nonadiabatic hydrogen tunneling regimes. The input quantities are computed using NEO density functional theory, which treats the transferring hydrogen or deuterium nucleus quantum mechanically on the same level as the electrons. We investigate two intramolecular proton transfer reactions in organic molecules at temperatures down to 50 K to evaluate the performance of NEO-GRT by comparison to transition state theory and ring-polymer instanton theory. The KIEs computed with NEO-GRT agree with those calculated using ring-polymer instanton theory for the full-dimensional molecular systems at the same level of electronic structure theory. This agreement indicates that NEO-GRT captures the deep hydrogen tunneling effects, in contrast to transition state theory, which neglects such effects. Given its relatively low computational cost, NEO-GRT is a promising approach for predicting H/D KIEs in large organic and organometallic systems.

Hydrogen↗
DOE OSTI2023

Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics

Practical methods for simulating photo-induced dynamics of molecules often rely on a trajectory-description of the nuclear dynamics, incorporating approximate electron-nuclear feedback. Through approximating electron–nuclear correlation terms in the exact factorization approach, trajectory-based methods have been derived and successfully applied to the dynamics of a variety of light-induced molecular processes, capturing quantum (de)coherence effects rigorously. These terms account for the coupling among the trajectories, recovering the nonlocal nature of quantum nuclear dynamics that is completely overlooked in traditional independent-trajectory algorithms. Nevertheless, some of the approximations introduced in the derivation of some of these methods do not conserve the total energy. We analyze energy conservation in the coupled trajectory mixed quantum-classical (CTMQC) algorithm and explore the performance of a modified algorithm, CTMQC-E, where some of the terms are redefined to restore energy conservation. Here, a set of molecular models is used as a test, namely, 2-cis-penta-2,4-dienimium cation, bis(methylene) adamantyl radical cation, butatriene cation, uracil radical cation, and neutral pyrazine.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Transition to unstable ion flow in parallel electric fields

The stability of ionospheric O(+)-H(+) outflows accelerated by a nonambipolar parallel electric field is considered under conditions where the ion motion initially develops adiabatically and the ambient plasma is vertically stratified with an effective temperature that increases with altitude. Such conditions are expected near the bottom of the auroral acceleration region where ion and electron streaming instabilities first develop. It is shown for a particular equilibrium profile that the differentially accelerated ion flows become unstable within about 100 km from their entry point in the acceleration region. At O(+)/H(+) density ratios less than about 9, the instability is dominated by a violent H(+)-O(+) two-stream interaction which couples the O(+) and H(+) acoustic modes, and which mediates a transition to nonadiabatic acceleration. At higher altitudes and/or larger O(+)/H(+) density ratios, a much weaker resonant instability exists, which is driven by the relative drift between electrons and O(+) or H(+) ions. The results suggest that the H(+)-O(+) two-stream instability may be a viable mechanism for heating upflowing auroral ions.

Bergmann, R.↗
DOE OSTI2020

Influence of tungsten doping on nonradiative electron–hole recombination in monolayer MoSe 2 with Se vacancies

Two-dimensional transition metal dichalcogenides (TMDs) are receiving significant attention due to their excellent electronic and optoelectronic properties. The material quality is greatly affected by defects that are inevitably generated during material synthesis. Focusing on chalcogenide vacancies, which constitute the most common defect, we use the state-of-the-art simulation methodology developed in our group to demonstrate that W doping of MoSe 2 with Se vacancies reduces charge carrier losses by two mechanisms. First, W doping makes the formation of double Se vacancies unfavorable, while it is favorable in undoped MoSe 2 . Second, if a Se vacancy is present, the charge carrier lifetimes are extended in the W-doped MoSe 2 . Combining ab initio real-time time-dependent density functional theory with nonadiabatic molecular dynamics, the simulations show that the nonradiative carrier losses in the presence of Se vacancies proceed by sub-10 ps electron trapping and relaxation down the manifold of trap states, followed by a 100 ps recombination of trapped electrons with free holes. The electron–vibrational energy exchange is driven by both in-plane and out-of-plane vibrational motions of the MoSe 2 layer. Additionally, the atomistic studies advance our understanding of the influence of defects on charge carrier properties in TMDs and guide improvements of material quality and development of TMD applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗