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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Quadrupolar magnetic excitations in an isotropic spin-1 antiferromagnet

The microscopic origins of emergent behaviours in condensed matter systems are encoded in their excitations. In ordinary magnetic materials, single spin-flips give rise to collective dipolar magnetic excitations called magnons. Likewise, multiple spin-flips can give rise to multipolar magnetic excitations in magnetic materials with spin S ≥ 1. Unfortunately, since most experimental probes are governed by dipolar selection rules, collective multipolar excitations have generally remained elusive. For instance, only dipolar magnetic excitations have been observed in isotropic S = 1 Haldane spin systems. Here, we unveil a hidden quadrupolar constituent of the spin dynamics in antiferromagnetic S = 1 Haldane chain material Y 2 BaNiO 5 using Ni L 3 -edge resonant inelastic x-ray scattering. Our results demonstrate that pure quadrupolar magnetic excitations can be probed without direct interactions with dipolar excitations or anisotropic perturbations. Originating from on-site double spin-flip processes, the quadrupolar magnetic excitations in Y 2 BaNiO 5 show a remarkable dual nature of collective dispersion. While one component propagates as non-interacting entities, the other behaves as a bound quadrupolar magnetic wave. This result highlights the rich and largely unexplored physics of higher-order magnetic excitations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Temporal coherent control of resonant two-photon double ionization of the hydrogen molecule via doubly excited states

Here, we use time-delayed, counter-rotating, circularly polarized few-cycle attosecond nonoverlapping pulses to study the temporal coherent control of the resonant process of two-photon double ionization (TPDI) of hydrogen molecule via doubly excited states for pulse propagation direction along $\hat k$ either parallel or perpendicular to the molecular axis $\hat R$. For $\hat k$∥ $\hat R$ and a pulse carrier frequency of 36 eV resonantly populating the Q 2 1 Π$^+_u$ (1) doubly excited state as well as other 1 Π$^+_u$ doubly excited states, we find that the indirect ionization pathway through these doubly excited states changes the character of the kinematical vortex-shaped momentum distribution produced by the two direct ionization pathways from fourfold to twofold rotational symmetry. This result is similar to what found in TPDI of the He atom involving 1 P$^ o_ {±1}$ doubly excited states; however, angular distributions exhibiting a quantum beat effect between the ground state and a doubly excited state seen for the He atom are observed here for its molecular counterpart with an anomaly in shape and magnitude, not in frequency. The sixfold differential probability integrated over the azimuthal angle of the photoelectron pair shows that this anomaly is due to autoionization decays and quantum beats between doubly excited states. For $\hat k$⟂$\hat R$ and a broadband pulse carrier frequency of 30 eV populating the Q 1 1 Π$^+_u$(1), Q 1 1 Σ$^+_u$(1), Q 2 1 Π$^+_u$(1) , and Q 1 1 Σ$^+_u$ (2) doubly excited states, the momentum distribution is shown to exhibit dynamical electron vortices with four spiral arms, which originates from the interplay between the 1 Δ$^+_ g$ , 1 Π$^+_ g$, and 1 Σ$^+_ g$ dynamical ionization amplitudes. Our treatment within either the adiabatic-nuclei approximation or fixed-nuclei approximation shows that the latter provides a very good account for this correlated process.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Analytic Gradients for Equation-of-Motion Coupled Cluster with Single, Double, and Perturbative Triple Excitations

Understanding the process of molecular photoexcitation is crucial in various fields, including drug development, materials science, photovoltaics, and more. The electronic vertical excitation energy is a critical property, for example in determining the singlet-triplet gap of chromophores. However, a full understanding of excited-state processes requires additional explorations of the excited-state potential energy surface and electronic properties, which is greatly aided by the availability of analytic energy gradients. Owing to its robust high accuracy over a wide range of chemical problems, equation-of-motion coupled-cluster with single and double excitations (EOM-CCSD) is a powerful method for predicting excited state properties, and the implementation of analytic gradients of many EOM-CCSD (excitation energies, ionization potentials, electron attachment energies, etc.) along with numerous successful applications high- lights the flexibility of the method. In specific cases where a higher level of accuracy is needed or in more complex electronic structures, the inclusion of triple excitations becomes essential, for example, in the EOM-CCSD* approach of Saeh and Stanton. In this work, we derive and implement for the first time the analytic gradients of EOMEE-CCSD*, which also provides a template for analytic gradients of related ex- cited state methods with perturbative triple excitations. Here, the capabilities of analytic EOMEE-CCSD* gradients are illustrated by several representative examples.

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

Benchmarking third-order cluster perturbation theory for electronically excited states

In this study, we investigate the reliability of cluster perturbation (CP) theory applied to the calculation of electronically excited states through a comprehensive benchmark. In CP theory, perturbative corrections are added to the properties of a parent excitation space, which converge toward the properties of a target excitation space. For the CPS(D-n) model, perturbative corrections through order n are added to the coupled cluster singles (CCS) excitation energies to target the coupled cluster singles and doubles (CCSD) excitation energies. Through a comparative analysis of excitation energy calculations across a diverse set of molecules and wavefunction methods, we present a comprehensive evaluation of the accuracy of the third-order CPS(D) model, CPS(D-3), in calculating excitation energies. Further, our findings demonstrate that CPS(D-3) is a reliable alternative to established methods, particularly CCSD, while systematically overestimating the excitation energies compared to high-level coupled cluster methods such as CC3. These results highlight the strengths and limitations of CPS(D-3), as well as the promising directions for its future development.

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

N 2 vibrational excitation in atmospheric pressure ns pulse and RF plasma jets

Time-resolved N 2 vibrational temperature and translational–rotational temperature in quasi-two-dimensional atmospheric pressure plasma jets sustained by ns pulse and RF discharges in nitrogen/noble gas mixtures are measured by the broadband vibrational Coherent Anti-Stokes Raman Scattering (CARS) . The results indicate a much stronger vibrational excitation in the RF plasma jet, due to the lower reduced electric field and higher discharge power. In a ns pulse discharge in N 2 /He, N 2 vibrational temperature is significantly lower compared to that in N 2 /Ar, due to the more rapid vibration–translation (V–T) relaxation of nitrogen by helium atoms. In the RF plasma jets in N 2 /Ne and N 2 /Ar, the vibrational excitation increases considerably as the nitrogen fraction in the mixture is reduced. The experimental data in the RF plasma jet in N 2 /Ar jet are compared with the kinetic modeling predictions. The results indicate that nitrogen vibrational excitation in N 2 /Ar plasma jets with a small N 2 fraction in the mixture (several percent) is controlled primarily by electron impact, anharmonic vibration–vibration (V–V) pumping, and V–T relaxation by N atoms. In comparison, V–V energy transfer from the vibrationally excited molecules in the first excited electronic state, N 2 (A 3 Σ u + , v), which are generated primarily by the energy transfer from the metastable Ar atoms, has a minor effect on the vibrational populations of the ground electronic state, N 2 (X 1 Σ g + , v). Although the discharge energy fraction going to electronic excitation is significant, the predicted quasi-steady-state N 2 (A 3 Σ u + ) number density, controlled by the energy pooling and quenching by N atoms, remains relatively low. Because of this, the net rate of N 2 (X 1 Σ g + ) vibrational excitation by the V–V energy transfer from N 2 (A 3 Σ u + ) is much lower compared to that by the direct electron impact. Furthermore, the results show that atmospheric pressure RF plasma jets can be used as sources of highly vibrationally excited N 2 molecules and N atoms.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Sterically Encumbered Heteroleptic Copper(I) β-Diketiminate Complexes with Extended Excited-State Lifetimes

One of the main challenges in developing effective copper(I) photosensitizers is their short excited-state lifetimes, usually attributed to structural distortion upon light excitation. We have previously introduced copper(I) charge-transfer chromophores of the general formula Cu(N^N)(ArNacNac), where N^N is a conjugated diimine ligand and ArNacNac is a substituted β-diketiminate ligand. These chromophores were promising regarding their tunable redox potentials and intense visible absorption but were ineffective as photosensitizers, presumably due to short excited-state lifetimes. Here, we introduce sterically crowded analogues of these heteroleptic chromophores with bulky alkyl substituents on the N^N and/or ArNacNac ligand. Structural analysis was combined with electrochemical and photophysical characterization, including ultrafast transient absorption (UFTA) spectroscopy to investigate the effects of the alkyl groups on the excited-state lifetimes of the complexes. The molecular structures determined by single-crystal X-ray diffraction display more distortion in the ground state as alkyl substituents are introduced into the phenanthroline or the NacNac ligand, showing smaller τ 4 values due to the steric hindrance. UFTA measurements were carried out to determine the excited-state dynamics. Sterically encumbered Cu5 and Cu6 display excited-state lifetimes 15–20 times longer than unsubstituted complex Cu1, likely indicating that the incorporation of bulky alkyl substituents inhibits the pseudo-Jahn–Teller (PJT) flattening distortion in the excited state. Furthermore, this work suggests that the steric properties of these heteroleptic copper(I) charge-transfer chromophores can be readily modified and that the excited-state dynamics are strongly responsive to these modifications.

14 SOLAR ENERGY↗
DOE OSTI2020

Ultrafast Dynamics of Excited Electronic States in Nitrobenzene Measured by Ultrafast Transient Polarization Spectroscopy

We investigate ultrafast dynamics of the lowest singlet excited electronic state in liquid nitrobenzene using ultrafast transient polarization spectroscopy, extending the well-known technique of optical Kerr effect spectroscopy to excited electronic states. The third-order nonlinear response of the excited molecular ensemble is measured using a pair of femtosecond pulses following a third femtosecond pulse that populates the S 1 excited state. By measuring this response, which is highly sensitive to details of the excited state character and structure, as a function of time delays between the three pulses involved, we extract the dephasing time of the wave packet on the excited state. The dephasing time, measured as a function of time delay after pump excitation, shows oscillations indicating oscillatory wave packet dynamics on the excited state. Finally, from the experimental measurements and supporting theoretical calculations, we deduce that the wave packet completely leaves the S 1 state potential energy surface after three traversals of the intersystem crossing between the singlet S 1 and triplet T 2 states.

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

Excited state electronic structure of dimethyl disulfide involved in photodissociation at ∼200 nm

Dimethyl disulfide (DMDS), one of the smallest organic molecules with an S–S bond, serves as a model system for understanding photofragmentation in polypeptides and proteins. Prior studies of DMDS photodissociation excited at ∼266 nm and ∼248 nm have elucidated the mechanisms of S–S and C–S bond cleavage, which involve the lowest excited electronic states S 1 and S 2 . Far less is known about the dissociation mechanisms and electronic structure of relevant excited states of DMDS excited at ∼200 nm. Herein we present calculations of the electronic structure and properties of electronic states S 1 –S 6 accessed when DMDS is excited at ∼200 nm. Our analysis includes a comparison of theoretical and experimental UV spectra, as well as theoretically predicted one-dimensional cuts through the singlet and triplet potential energy surfaces along the S–S and C–S bond dissociation coordinates. Finally, we present calculations of spin–orbit coupling constants at the Franck–Condon geometry to assess the likelihood of ultrafast intersystem crossing. We show that choosing an accurate yet computationally efficient electronic structure method for calculating the S 0 –S 6 potential energy surfaces along relevant dissociation coordinates is challenging due to excited states with doubly excited character and/or mixed Rydberg-valence character. Our findings demonstrate that the extended multi-state complete active space second-order perturbation theory (XMS-CASPT2) balances this computational efficiency and accuracy, as it captures both the Rydberg character of states in the Franck–Condon region and multiconfigurational character toward the bond-dissociation limits. In conclusion, we compare the performance of XMS-CASPT2 to a new variant of equation of motion coupled cluster theory with single, double, and perturbative triple corrections, EOM-CCSD(T)(a)*, finding that EOM-CCSD(T)(a)* significantly improves the treatment of doubly excited states compared to EOM-CCSD, but struggles to quantitatively capture asymptotic energies along bond dissociation coordinates for these states.

Rishi, Varun↗
DOE OSTI2022

Resonant double-core excitations with ultrafast, intense X-ray pulses

Intense few-to-sub-femtosecond soft X-ray pulses can produce neutral, two-site excited double-core-hole states by promoting two core electrons to the same unoccupied molecular orbital. We theoretically investigate double nitrogen K-edge excitations of nitrous oxide (N$_2$O) with multiconfigurational electronic structure calculations. We show that the second core-excitation energy is reduced with respect to its ground state value. A site-selective double core-excitation mechanism using intense few-femtosecond x-rays is investigated using time-dependent Schrodinger equation (TDSE) simulations. The subsequent two-step Auger-Meitner and two-electrons-one-electron decay spectra of the double core-excited states are analysed using a Mulliken population analysis of the multiconfirational wavefunctions. The change in the electron emission lineshape between the absorption of 1 or 2 photons in the resonant core-excitation is predicted by combining this approach with the TDSE simulations. Furthermore, we examine the possibility of resolving the double core-excited states with X-ray pump-probe techniques by calculating the chemical shifts of the core-electron binding energy of the core-excited states and decay products.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Luminescent Zr Complexes with Long-lived Intraligand Charge Transfer Excited States

Understanding and establishing design principles to tune the excited states of earth-abundant sensitizers is crucial for identifying new photosensitizers for sustainable technological advancements. Here, we report a series of three bis Zr (IV) complexes of tridentate, dianionic ligands incorporating two phenoxide donors and aza arene acceptors of increasing electron affinity (pyridine < pyrimidine < pyrazine ) that are air and water-stable. These complexes emit via thermally assisted delayed fluorescence from an intraligand charge transfer excited state with varying metal contributions. The electronic structural changes from different acceptors vary the excited state character and the photophysical properties significantly between the complexes. The variation in photophysics that includes emission lifetime (76 μs to 265 ns), intersystem crossing (ISC) lifetime ( 390 – 290 ps), and the energy difference between the singlet and triplet excited states (∆EST. 170 -100 meV). We observe solvent-independent ISC rates when the excited state has metal contributions (acceptor = pyridine), and the ISC rates vary significantly with solvent polarity when the excited state is an intra-ligand charge transfer state (acceptor = pyrimidine and pyrazine). Transient absorption measurements provided the basis spectra and verified the metal contribution in the excited state. This work provides a basis for developing new sensitizers based on Zr (IV) by providing design principles that can be used to modulate the character of the excited state and its photophysics.

Nattikallungal, Thabassum A. [University of Southe↗
DOE OSTI2020

Method for dynamic control of light emission from phosphors with heat excitations

An optically emissive material and, in particular, materials for use in single photon generation technologies, have multiple excited energy states that have different decay rates and can emit photons with different properties. A primary excitation radiation source is configured to apply primary radiation to an optically emissive material to excite the optically emissive material into a primary excited state. A secondary excitation radiation source is configured to apply secondary radiation to a thermal contribution material to generate thermal energy in the thermal contribution material. The thermal contribution material is physically configured to transfer thermal energy to the optically emissive material and excite the optically emissive material from the primary excited state to a secondary excited state for dynamic control of the emission rate, or emitted photon properties, of the optically emissive material.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Excitation Laser Energy Dependence of the Gap-Mode TERS Spectra of WS 2 and MoS 2 on Silver

In this work we present a systematic study of the dependence of the gap mode tip-enhanced Raman scattering (TERS) response of the mono- and bi-layer WS 2 and MoS 2 on silver as a function of the excitation laser energy in a broad spectral range from 473nm to 830 nm. For this purpose, we collected consecutive TERS maps of the same area in the sample containing mono-and bi-layer regions with the same TERS probe with 6 different excitation lasers. To decrease the number of collected TERS maps, we used for the first time to the best of our knowledge, concurrent excitation and collection with two lasers simultaneously. We found that the E 2g /A 1g peak intensity ratio for the bilayer WS 2 @Ag and the ratio of the A’/A 1g peak intensity of the out-of-plane mode for the mono- and the bilayer, change in a significantly non-monotonous way as the excitation laser energy is swept from 1.58 eV to 2.62 eV. The former ratio increases at energies corresponding to A and B excitons (~2.0 eV and 2.4 eV correspondingly) in bilayer WS 2 . The absolute intensity of the A’ peak in the monolayer, and correspondingly the A’/A 1g ratio, is surprisingly high at lower excitation energies, but dips dramatically at the energy corresponding to the A exciton, being restored partially in between A and B excitons, but still showing the descending trend as the excitation laser energy increases. A somewhat similar picture was observed in mono- and bi-layers of MoS 2 @Ag, though the existing set of excitation lasers did not match the excitonic profile of this material as nicely as for the case of WS 2 . We attribute the observed behavior to the presence of intermediate (Fano resonance) or strong (Rabi splitting) coupling between the excitons in transition metal dichalcogenides (TMDs) and the plasmons in the tip-substrate nanocavity. This is akin to the so-called Fano (Rabi) transparency experimentally observed in far field scattering from transition metal dichalcogenides between two plasmonic metals. The possibility of the formation of intermediate/strong coupling between the excitonic resonances in TMDs and the nanocavity re-evaluates the role of various resonances in the gap-mode TERS and should become an important factor to be considered by TERS practitioners during planning the experiments. Lastly, based on observed phenomena and its explanation, we propose the “ideal” substrate for efficient TERS and tip enhanced photoluminescence (TEPL) measurements.

Raman spectroscopy↗
DOE OSTI2025

Excited-State Densities from Time-Dependent Density Functional Response Theory

While the variational principle for excited-state energies leads to a route to obtaining excited-state densities from time-dependent density functional theory, relatively little attention has been paid to the quality of the resulting densities in real space obtained with different exchange-correlation functional approximations or how nonadiabatic approximations developed for energies of states of double-excitation character perform for their densities. Here we derive an expression directly in real space for the excited-state density, which includes the case of nonadiabatic kernels and consequently is able, for the first time, to yield densities of states of double-excitation character. Under some well-defined simplifications, we compare the performance of the local-density approximation and exact-exchange approximation, which are in a sense at the opposite extremes of the fundamental functional approximations, on local and charge-transfer excitations in one-dimensional model systems and show that the dressed Time-Dependent Density Functional Theory (TDDFT) approach gives good densities of double excitations.

approximation↗
DOE OSTI2022

Observation of Core-Excited Dipole-Bound States

Polar molecules can bind an electron in a diffuse orbital due to the charge-dipole interaction. Electronic excited states of polar molecules can also bind an electron to form core-excited dipole-bound states (DBSs), analogous to core-excited Rydberg states. However, core-excited DBSs have not been observed because of the complicated electronic structure of molecular systems. Here we report the observation of a core-excited DBS in the pyrazolide anion as a result of the favorable electronic structure of the neutral pyrazolyl core, which has a low-lying excited state ($\tilde{A}$ 2 B 1 ) only 266 cm -1 above its ground state ($\tilde{X}$ 2 A 2 ). The binding energy of the DBS associated with the ground state is measured to be 221 cm -1 , while that of the core-excited DBS is 276 cm -1 , which is still a bound state relative to the detachment threshold. Furthermore, vibrational Feshbach resonances are observed for both DBSs and their autodetachment behaviors are studied by resonant photoelectron imaging.

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

Measuring Intermolecular Excited State Geometry for Favorable Singlet Fission in Tetracene

Singlet fission (SF) is the process of converting an excited singlet to a pair of excited triplets. Harvesting two charges from a single photon has the potential to increase photovoltaic device efficiencies. Acenes, such as tetracene and pentacene, are model molecules for studying SF. Despite SF being an endoergic process for tetracene and exoergic for pentacene, both acenes exhibit near unity SF quantum efficiencies, raising questions about how tetracene can overcome the energy barrier. Here, we use recently developed instrumentation to measure inelastic neutron scattering (INS) while optically exciting the model molecules using two different excitation energies. The spectroscopic results reveal intermolecular structural relaxation due to the presence of a triplet excited state. Here, the structural dynamics of the combined excited state molecule and surrounding tetracene molecules are further studied using time-dependent density functional theory (TD-DFT), which shows that the singlet and triplet levels shift due to the excited state geometry, reducing the uphill energy barrier for SF to within kT.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons

This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are used to identify 1-Pyreneacetic acid as a molecule with this property and the dynamics of ESVP are modeled. Overall, this work introduces an avenue of polariton chemistry where excited state dynamics are influenced by the formation of vibrational polaritons. Along with this, the UV/vis-to-IR photonic down conversion is potentially useful in both sensing excited state vibrations and quantum transduction schemes.

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

Excited-State Dynamics of All the Mono-cis and the Major Di-cis Isomers of β-Apo-8′-Carotenal as Revealed by Femtosecond Time-Resolved Transient Absorption Spectroscopy

Cis isomers of carotenoids play important roles in light harvesting and photoprotection in photosynthetic bacteria, such as the reaction center in purple bacteria and the photosynthetic apparatus in cyanobacteria. Carotenoids containing carbonyl groups are involved in efficient energy transfer to chlorophyll in light-harvesting complexes, and their intramolecular charge–transfer (ICT) excited states are known to be important for this process. Previous studies, using ultrafast laser spectroscopy, have focused on the central-cis isomer of carbonyl-containing carotenoids, revealing that the ICT excited state is stabilized in polar environments. However, the relationship between the cis isomer structure and the ICT excited state has remained unresolved. In this study, we performed steady-state absorption and femtosecond time-resolved absorption spectroscopy on nine geometric isomers (7-cis, 9-cis, 13-cis, 15-cis, 13′-cis, 9,13′-cis, 9,13-cis, 13,13′-cis, and all-trans) of β-apo-8′-carotenal, whose structures are well-defined, and discovered correlations between the decay rate constant of the S1 excited state and the S0−S1 energy gap, as well as between the position of the cis-bend and the degree of stabilization of the ICT excited state. Our results demonstrate that the ICT excited state is stabilized in polar environments in cis isomers of carbonyl-containing carotenoids and suggest that the position of the cis-bend plays an important role in the stabilization of the excited state.

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

A comparison of strategies for state-selective coherent Raman excitation

Here we report on the theoretical and experimental evaluation of state-selective bond activation for coherent Raman spectroscopy and control of chemical reactivity. We compare six different strategies for state-selective activation using shaped broadband femtosecond laser pulses. Results for a pair of long pulses with different wavelengths are also considered. For each of these approaches, we report on their theoretical and experimental ability to excite a desired vibrational mode while minimizing excitation of other modes including harmonics. We find that the double parabola spectral phase function gives the most intense Raman excitation with 10 cm -1 selectivity with the lowest background. The sinusoidal phase function produces intense Raman excitation with high selectivity but gives a series of harmonic excitations which could hinder selectivity. Implications of this study on several fields ranging from sensing, to controlling chemical reactions, and selective excited state excitation by X-ray pulses are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗