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Results for “RADIATIONLESS DECAY”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Laser control of the radiationless decay in pyrazine using the dynamic Stark effect

The laser control of the radiationless decay between the B{sub 3u}(nπ*) and B{sub 2u}(ππ*) states of pyrazine using the dynamic Stark effect has been investigated. A vibronic coupling model Hamiltonian in diabatic representation, including potential energy, transition dipole, and static polarizability surfaces as a function of the four most important vibrational modes of the molecule has been parametrized using multi-reference electronic structure calculations. The interaction of the molecule with a strong non-resonant laser pulse has been analyzed in terms of dressed potential energy surfaces. Because of the large polarizability difference between the vibronically coupled B{sub 3u}(nπ*) and B{sub 2u}(ππ*) states, the Stark effect induced by the non-resonant laser pulse shifts the conical intersection away from the Franck-Condon region. We have shown, by solving the time-dependent Schrödinger equation for the molecule interacting with a relatively weak pump pulse driving the electronic excitation from the ground state to the B{sub 2u}(ππ*) state, and a strong non-resonant control pulse, that this control mechanism can be used to trap the wavepacket on the B{sub 2u}(ππ*) potential energy surface for a much longer time than the natural B{sub 2u}(ππ*) lifetime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Full-dimensional control of the radiationless decay in pyrazine using the dynamic Stark effect

We present a full quantum-mechanical study of the laser control of the radiationless decay between the B{sub 3u}(nπ{sup *}) and B{sub 2u}(ππ{sup *}) states of pyrazine using the dynamic Stark effect. In contrast to our previous study [Sala et al., J. Chem. Phys. 140, 194309 (2014)], where a four-dimensional model was used, all the 24 degrees of freedom are now included in order to test the robustness of the strategy of control. Using a vibronic coupling Hamiltonian model in a diabatic representation, the multi-layer version of the multi-configuration time-dependent Hartree method is exploited to propagate the corresponding wave packets. We still observe a trapping of the wavepacket on the B{sub 2u}(ππ{sup *}) potential energy surface due to the Stark effect for a longer time than the “non-resonant field-free” B{sub 2u}(ππ{sup *}) lifetime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S{sub 2} state

The trans-urocanic acid, a UV chromophore in the epidermis of human skin, was found to exhibit a wavelength dependent isomerization property. The isomerization quantum yield to cis-urocanic is greatest when being excited to the S{sub 1} state, whereas exciting the molecule to the S{sub 2} state causes almost no isomerization. The comparative photochemical behavior of the trans-urocanic on the S{sub 1} and S{sub 2} states continues to be the subject of intense research effort. This study is concerned with the unique photo-behavior of this interesting molecule on the S{sub 2} state. Combining the on-the-fly surface hopping dynamics simulations and static electronic structure calculations, three decay channels were observed following excitation to the S{sub 2} state. An overwhelming majority of the molecules decay to the S{sub 1} state through a planar or pucker characterized minimum energy conical intersection (MECI), and then decay to the ground state along a relaxation coordinate driven by a pucker deformation of the ring. A very small fraction of molecules decay to the S{sub 1} state by a MECI characterized by a twisting motion around the CC double bond, which continues to drive the molecule to deactivate to the ground state. The latter channel is related with the photoisomerization process, whereas the former one will only generate the original trans-form products. The present work provides a novel S{sub 2} state decay mechanism of this molecule, which offers useful information to explain the wavelength dependent isomerization behavior.

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

Quantum dynamics on a three-sheeted six-dimensional ab initio potential-energy surface of the phosphine cation: Simulation of the photoelectron spectrum and the ultrafast radiationless decay dynamics

A diabatic three-sheeted six-dimensional potential-energy surface has been constructed for the ground state and the lowest excited state of the PH{sub 3}{sup +} cation. Coupling terms of Jahn-Teller and pseudo-Jahn-Teller origin up to eighth order had to be included to describe the pronounced anharmonicity of the surface due to multiple conical intersections. The parameters of the diabatic Hamiltonian have been optimized by fitting the eigenvalues of the potential-energy matrix to ab initio data calculated at the CASSCF/MRCI level employing the correlation-consistent triple-ζ basis. The theoretical photoelectron spectrum of phosphine and the non-adiabatic nuclear dynamics of the phosphine cation have been computed by propagating nuclear wave packets with the multiconfiguration time-dependent Hartree method. The theoretical photoelectron bands obtained by Fourier transformation of the autocorrelation function agree well with the experimental results. It is shown that the ultrafast non-radiative decay dynamics of the first excited state of PH{sub 3}{sup +} is dominated by the exceptionally strong Jahn-Teller coupling of the asymmetric bending vibrational mode together with a hyperline of conical intersections with the electronic ground state induced by the umbrella mode. Time-dependent population probabilities have been computed for the three adiabatic electronic states. The non-adiabatic Jahn-Teller dynamics within the excited state takes place within ≈5 fs. Almost 80% of the excited-state population decay to the ground state within about 10 fs. The wave packets become highly complex and delocalized after 20 fs and no further significant transfer of electronic population seems to occur up to 100 fs propagation time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Long-lived two-dimensional triplet magnetoexcitons in a Hall insulator

An experimental technique is developed to perform photoexcitation of an ensemble of translationinvariant triplet excitons, to manipulate this ensemble, and to detect the properties of its components. In particular, the influence of temperature on the radiationless decay during the relaxation of an exciton spin into the ground state of a Hall insulator at a filling factor ν = 2 is studied. The generation of photoexcited electrons and holes is controlled using photoinduced resonance reflection spectra, which makes it possible to estimate the density of light-generated electron–hole pairs and to independently control the self-consistent generation of electrons at the first Landau level and holes (vacancies) at the ground (zero) cyclotron electronic level. The existence of triplet excitons is established from inelastic light scattering spectra, which are used to determine the singlet–triplet exciton splitting. The lifetimes of triplet excitons, which are closely related to the relaxation time of an electron spin, are extremely long: they reach 100 μs in perfect GaAs/AlGaAs heterostructures with a high mobility of two-dimensional electrons at low temperatures. These long spin relaxation times are qualitatively explained, and the expected collective behavior of high-density triplet magnetoexcitons at sufficiently low temperatures, which is related to their Bose nature, is discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Up to a Sign. The Insidious Effects of Energetically Inaccessible Conical Intersections on Unimolecular Reactions

It is well established that conical intersections play an essential role in nonadiabatic radiationless decay where their double-cone topography causes them to act as efficient funnels channeling wave packets from the upper to the lower adiabatic state. Until recently, little attention was paid to the effect of conical intersections on dynamics on the lower state, particularly when the total energy involved is significantly below that of the conical intersection seam. This energetic deficiency is routinely used as a sufficient condition to exclude consideration of excited states in ground state dynamics. In this account, we show that, this energy criterion notwithstanding, energy inaccessible conical intersections can and do exert significant influence on lower state dynamics. The origin of this influence is the geometric phase, a signature property of conical intersections, which is the fact that the real-valued electronic wave function changes sign when transported along a loop containing a conical intersection, making the wave function double-valued. This geometric phase is permitted by an often neglected property of the real-valued adiabatic electronic wave function; namely, it is determined only up to an overall sign. Noting that in order to change sign a normalized, continuous function must go through zero, for loops of ever decreasing radii, demonstrating the need for an electronic degeneracy (intersection) to accompany the geometric phase. Since the total wave function must be single-valued a compensating geometry dependent phase needs to be included in the total electronic-nuclear wave function. This Account focuses on how this consequence of the geometric phase can modify nuclear dynamics energetically restricted to the lower state, including tunneling dynamics, in directly measurable ways, including significantly altering tunneling lifetimes, thus confounding the relation between measured lifetimes and barrier heights and widths, and/or completely changing product rotational distributions.

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

Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole

Three singlet states, namely a closed-shell ground state and two excited states with 1 ππ* and 1 nσ* character, have been suggested to be responsible for the radiationless decay or photochemical reaction of photoexcited thioanisole. The correct interpretation of the electronic spectrum is critical for understanding the character of these low-lying excited states, but the experimental spectrum is yet to be fully interpreted. In the work reported here, we investigated the nature of those three states and a fourth singlet state of thioanisole using electronic structure calculations by multireference perturbation theory, by completely-renormalized equation-of-motion coupled cluster theory with single and double excitations and noniterative inclusion of connected triples (CR-EOM-CCSD(T)), and by linear-response time-dependent density functional theory (TDDFT). We clarified the assignment of the electronic spectrum by simulating it using a normal-mode sampling approach combined with TDDFT in the Tamm–Dancoff approximation (TDA). The understanding of the electronic states and of the accuracy of the electronic structure methods lays the foundation of our future work of constructing potential energy surfaces.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Simulation of the photodetachment spectra of the nitrate anion (NO 3 ₋ ) in the B ~ 2 E' energy range and non-adiabatic electronic population dynamics of NO 3

The photodetachment spectrum of the nitrate anion (NO 3 ₋ ) in the energy range of the NO 3 second excited state is simulated from first principles using quantum wave packet dynamics. The prediction at 10 K and 435 K relies on the use of an accurate full-dimensional fully coupled five state diabatic potential model utilizing an artificial neural network. The ability of this model to reproduce experimental spectra was demonstrated recently for the lower energy range. Analysis of the spectra indicates a weaker Jahn–Teller coupling compared to the first excited state. The detailed non-adiabatic dynamics is studied by computing the population dynamics. An ultra-fast non-statistical radiationless decay is found only among the Jahn–Teller components, which is followed by a slow statistical non-radiative decay among the different state manifolds. The latter is reproduced perfectly by a simple first order kinetics model. The dynamics in the second excited state is not affected by the presence of a conical intersection with the first excited state manifold.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Efficient simulation of open quantum systems coupled to a reservoir through multiple channels

It is challenging to simulate open quantum systems that are connected to a reservoir through multiple channels. For example, vibrations may induce fluctuations in both energy gaps and electronic couplings, which represent two independent channels of system–bath couplings. Systems of this kind are ubiquitous in the processes of excited state radiationless decay. Combined with density matrix renormalization group (DMRG) and matrix product states (MPS) methods, we develop an interaction-picture chain mapping strategy for vibrational reservoirs to simulate the dynamics of these open systems, resulting in time-dependent spatially local system–bath couplings in the chain-mapped Hamiltonian. This transformation causes the entanglement generated by the system–bath interactions to be restricted within a narrow frequency window of vibrational modes, enabling efficient DMRG/MPS dynamical simulations. We demonstrate the utility of this approach by simulating singlet fission dynamics using a generalized spin-boson Hamiltonian with both diagonal and off-diagonal system–bath couplings. This approach generalizes an earlier interaction-picture chain mapping scheme, allowing for efficient and exact simulation of systems with multi-channel system–bath couplings using matrix product states, which may further our understanding of nonlocal exciton–phonon couplings in exciton transport and the non-Condon effect in energy and electron transfer.

Chemistry↗
DOE OSTI2014

Relativistic M-subshell radiationless transition probabilities and energies for Zn, Cd and Hg

Theoretical calculations of radiationless transition probabilities and energies for M-subshell vacancies in Zn, Cd, and Hg are tabulated using the Dirac–Fock method. Transition probabilities between an initial vacancy state and a final two-vacancies state are presented for each initial and final atomic angular momentum quantum number. Calculations were performed in the single configuration approach with the Breit interaction, self-energy and (Uehling) vacuum polarization corrections included in the self-consistent method. Higher-order retardation corrections and QED effects were also included as perturbations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

Calculations of photo-induced X-ray production cross-sections in the energy range 1–150 keV and average fluorescence yields for Zn, Cd and Hg

In this paper, we calculate the K-, L- and M-shells X-ray production, and X-ray fluorescence cross-sections after photo-induced ionization, for Zn, Cd, and Hg, and for incident photon energy range from 1 to 150 keV. For this purpose, the corresponding average fluorescence yields for Zn, Cd, and Hg as well as the photoionization cross-sections were calculated using the Dirac–Fock method. Subshell fluorescence, intrashell and intershell yields are obtained consistently from radiative and radiationless transitions calculated in the exact same method. A comprehensive account of the relations between the X-ray production, X-ray fluorescence cross-sections and the photoionization cross-sections and these yields is presented. Comparisons are made with results from other authors. The obtained values for the photoionization cross-sections are in good agreement with the widely used data of Scofield in the studied energy range. However our results for the X-ray fluorescence cross sections seem to favor some data relatively to others. The energy dependence of the average fluorescence yields is discussed, in particular, the reliability of extrapolated data for lighter elements from measurements and calculations in heavier elements above the inner shell absorption edges is questioned. Tabulated data on photoionization and X-ray production cross-sections are presented for the incident photon energy range 1–150 keV in steps of 1 keV.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

Full observation of ultrafast cascaded radiationless transitions from S{sub 2}(ππ{sup ∗}) state of pyrazine using vacuum ultraviolet photoelectron imaging

A photoexcited molecule undergoes multiple deactivation and reaction processes simultaneously or sequentially, which have been observed by combinations of various experimental methods. However, a single experimental method that enables complete observation of the photo-induced dynamics would be of great assistance for such studies. Here we report a full observation of cascaded electronic dephasing from S{sub 2}(ππ{sup *}) in pyrazine (C{sub 4}N{sub 2}H{sub 4}) by time-resolved photoelectron imaging (TRPEI) using 9.3-eV vacuum ultraviolet pulses with a sub-20 fs time duration. While we previously demonstrated a real-time observation of the ultrafast S{sub 2}(ππ{sup *}) → S{sub 1}(nπ{sup *}) internal conversion in pyrazine using TRPEI with UV pulses, this study presents a complete observation of the dynamics including radiationless transitions from S{sub 1} to S{sub 0} (internal conversion) and T{sub 1}(nπ{sup *}) (intersystem crossing). Also discussed are the role of {sup 1}A{sub u}(nπ{sup *}) in the internal conversion and the configuration interaction of the S{sub 2}(ππ{sup *}) electronic wave function.

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

Photoinduced hydrogen dissociation in thymine predicted by coupled cluster theory

The fate of thymine upon excitation by ultraviolet radiation has been the subject of intense debate. Today, it is widely believed that its ultrafast excited state gas phase decay stems from a radiationless transition from the bright ππ* state to a dark nπ* state. However, conflicting theoretical predictions have made the experimental data difficult to interpret. Here we simulate the early gas phase ultrafast dynamics in thymine at the highest level of theory to date. This is made possible by performing wavepacket dynamics with a recently developed coupled cluster method. Our simulation confirms an ultrafast ππ* to nπ* transition (τ = 41 ± 14 fs). Furthermore, the predicted oxygen-edge X-ray absorption spectra agree quantitatively with experiment. We also predict an as-yet uncharacterized πσ* channel that leads to hydrogen dissociation at one of the two N-H bonds. Similar behavior has been identified in other heteroaromatic compounds, including adenine, and several authors have speculated that a similar pathway may exist in thymine. However, this was never confirmed theoretically or experimentally. This prediction calls for renewed efforts to experimentally identify or exclude the presence of this channel.

Kjønstad, Eirik F.↗
DOE OSTI2014

Communication: Electron transfer mediated decay enabled by spin-orbit interaction in small krypton/xenon clusters

In this work we study the influence of relativistic effects, in particular spin-orbit coupling, on electronic decay processes in KrXe{sub 2} clusters of various geometries. For the first time it is shown that inclusion of spin-orbit coupling has decisive influence on the accessibility of a specific decay pathway in these clusters. The radiationless relaxation process is initiated by a Kr 4s ionization followed by an electron transfer from xenon to krypton and a final second ionization of the system. We demonstrate the existence of competing electronic decay pathways depending in a subtle way on the geometry and level of theory. For our calculations a fully relativistic framework was employed where omission of spin-orbit coupling leads to closing of two decay pathways. These findings stress the relevance of an adequate relativistic description for clusters with heavy elements and their fragmentation dynamics.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Photoswitching dynamics of a guanidine anion receptor

Photoswitchable molecules involving large-scale structural changes such as E/Z photoisomerization offer remarkable opportunities for light-stimulated catch-and-release chemical separations. While the feasibility of this photochemically driven mechanism has been demonstrated in pioneering studies, the electronic excited-state relaxation processes and concomitant structural changes of such a functional photoswitcher remain largely unexplored. Here, we investigate an exceptional photoswitchable molecule, 2-pyridyl-diiminoguanidinium (2PyDIG), which exhibits strong and selective anion binding, along with an extraordinary capability for light-induced release of a guest ion. Through time-resolved fluorescence measurements and multireference and time-dependent density functional theory calculations, we reveal the dynamics underlying electronic excited state relaxation and photoisomerization central to photoswitching. A very rapid and dominant decay component was found that is consistent with radiationless de-excitation from S 1 to S 0 through conical intersections. This process competes effectively with the slower photoisomerization process taking place in 94 ps. We further identified the underlying causes through theoretical calculations and potential routes towards improved photoisomerization efficiencies.

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

A simple generalization of the energy gap law for nonradiative processes

For more than 50 years, an elegant energy gap (EG) law developed by Englman and Jortner [Mol. Phys. 18, 145 (1970)] has served as a key theory to understand and model the nearly exponential dependence of nonradiative transition rates on the difference of energy between the initial and final states. This work revisits the theory, clarifies the key assumptions involved in the rate expression, and provides a generalization for the cases where the effects of temperature dependence and low-frequency modes cannot be ignored. For a specific example where the low-frequency vibrational and/or solvation responses can be modeled as an Ohmic spectral density, a simple generalization of the EG law is provided. Test calculations demonstrate that this generalized EG law brings significant improvement over the original EG law. Both the original and generalized EG laws are also compared with the stationary phase approximations developed for electron transfer theory, which suggests the possibility of a simple interpolation formula valid for any value of EG.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Evolution of Excited-State Dynamics in Periodic Au 28 , Au 36 , Au 44 , and Au 52 Nanoclusters

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28 , Au 36 , Au 44 , and Au 52 ), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacks ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.

36 MATERIALS SCIENCE↗