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Results for “Rydberg State”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Exotic Photonic Molecules via Lennard-Jones-like Potentials

Ultracold systems offer an unprecedented level of control of interactions between atoms. An important challenge is to achieve a similar level of control of the interactions between photons. Towards this goal, we propose a realization of a novel Lennard-Jones-like potential between photons coupled to the Rydberg states via electromagnetically induced transparency (EIT). This potential is achieved by tuning Rydberg states to a Förster resonance with other Rydberg states. In this work, we consider few-body problems in 1D and 2D geometries and show the existence of self-bound clusters (“molecules”) of photons. We demonstrate that for a few-body problem, the multibody interactions have a significant impact on the geometry of the molecular ground state. This leads to phenomena without counterparts in conventional systems: For example, three photons in two dimensions preferentially arrange themselves in a line configuration rather than in an equilateral-triangle configuration. Our result opens a new avenue for studies of many-body phenomena with strongly interacting photons.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Pathways to excitation of atoms with bicircular laser pulses

We study the excitation of the hydrogen atom by bichromatic circularly polarized laser pulses using numerical solutions of the time-dependent Schrödinger equation. The results are in agreement with the selection rules for multiphoton processes in such fields, namely, excited states are populated in which orbital angular momentum and magnetic quantum numbers are either both odd or both even, independent of the relative helicity, peak intensity, and pulse duration of the pulses. For co-rotating pulses the results show that excitation predominantly proceeds to states with magnetic quantum number of the same helicity as the laser pulses. Besides pathways via direct photon absorption from the ground state our results indicate that a transfer of population among the Rydberg states occurs via Λ-type transitions. In the case of counter-rotating pulses the largest excitation probability is found for Rydberg states that differ in magnetic quantum number by Δm=±3. This pattern allows us to estimate how many photons from each of the two bichromatic fields have been absorbed. Finally, we confirm that a population in Rydberg states beyond a maximum orbital angular quantum number is unlikely.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Nonclassical light from finite-range interactions in a two-dimensional quantum mirror

Excitons in a semiconductor monolayer form a collective resonance that can reflect resonant light with extraordinarily high efficiency. We investigate the nonlinear optical properties of such atomistically thin mirrors and show that finite-range interactions between excitons can lead to the generation of highly nonclassical light. We describe two scenarios, in which optical nonlinearities arise either from direct photon coupling to excitons in excited Rydberg states or from resonant two-photon excitation of Rydberg excitons with finite-range interactions. The latter case yields conditions of electromagnetically induced transparency and thereby provides an efficient mechanism for single-photon switching between high transmission and reflectance of the monolayer, with a tunable dynamical timescale of the emerging photon-photon interactions. Remarkably, it turns out that the resulting high degree of photon correlations remains virtually unaffected by Rydberg-state decoherence, in excess of nonradiative decoherence observed for ground-state excitons in two-dimensional semiconductors. This robustness to imperfections suggests a promising approach to quantum photonics at the level of individual photons.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Resonant two-photon photoelectron imaging and adiabatic detachment processes from bound vibrational levels of dipole-bound states

Anions cannot have Rydberg states, but anions with polar neutral cores can support highly diffuse dipole-bound states (DBSs) as a class of interesting electronically excited states below the electron detachment threshold. The binding energies of DBSs are extremely small, ranging from a few to few hundred wavenumbers and generally cannot support bound vibrational levels below the detachment threshold. Thus, vibrational excitations in the DBS are usually above the electron detachment threshold and they have been used to conduct resonant photoelectron spectroscopy, which is dominated by state-specific autodetachment. Here we report an investigation of a cryogenically-cooled complex anion, the enantiopure (R)-(–)-1-(9-anthryl)-2,2,2-trifluoroethanolate (R-TFAE–). The neutral R-TFAE radical is relatively complex and highly polar with a non-planar structure (C 1 symmetry). Photodetachment spectroscopy reveals a DBS 209 cm–1 below the detachment threshold of R-TFAE– and seven bound and eight above-threshold vibrational levels of the DBS. Resonant two-photon detachment (R2PD) via the bound vibrational levels of the DBS exhibits strictly adiabatic photodetachment behaviors by the second photon, in which the vibrational energies in the DBS are carried to the neutral final states, because of the parallel potential energy surfaces of the DBS and the corresponding neutral ground electronic state. Relaxation processes from the bound DBS levels to the ground and low-lying electronically excited states of R-TFAE– are also observed in the R2PD photoelectron spectra. Finally, the combination of photodetachment and resonant photoelectron spectroscopy yields frequencies for eight vibrational modes of the R-TFAE radical.

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

Laser spectroscopy of indium Rydberg atom bunches by electric field ionization

This work reports on the application of a novel electric field-ionization setup for high-resolution laser spectroscopy measurements on bunched fast atomic beams in a collinear geometry. In combination with multi-step resonant excitation to Rydberg states using pulsed lasers, the field ionization technique demonstrates increased sensitivity for isotope separation and measurement of atomic parameters over previous non-resonant laser ionization methods. The setup was tested at the Collinear Resonance Ionization Spectroscopy experiment at ISOLDE-CERN to perform high-resolution measurements of transitions in the indium atom from the 5s 2 5d 2 D 5/2 and 5s 2 5d 2 D 3/2 states to 5s 2 np 2 P and 5s 2 nf 2 F Rydberg states, up to a principal quantum number of n=72 . The extracted Rydberg level energies were used to re-evaluate the ionization potential of the indium atom to be 46,670.107(4)cm -1 . The nuclear magnetic dipole and nuclear electric quadrupole hyperfine structure constants and level isotope shifts of the 5s 2 5d 2 D 5/2 and 5s 2 5d 2 D 3/2 states were determined for 113,115 In. The results are compared to calculations using relativistic coupled-cluster theory. A good agreement is found with the ionization potential and isotope shifts, while disagreement of hyperfine structure constants indicates an increased importance of electron correlations in these excited atomic states. With the aim of further increasing the detection sensitivity for measurements on exotic isotopes, a systematic study of the field-ionization arrangement implemented in the work was performed at the same time and an improved design was simulated and is presented. The improved design offers increased background suppression independent of the distance from field ionization to ion detection.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Excited State Orbital Optimization via Minimizing the Square of the Gradient: General Approach and Application to Singly and Doubly Excited States via Density Functional Theory

We present a general approach to converge excited state solutions to any quantum chemistry orbital optimization process, without the risk of variational collapse. The resulting square gradient minimization (SGM) approach only requires analytic energy/Lagrangian orbital gradients and merely costs 3 times as much as ground state orbital optimization (per iteration), when implemented via a finite difference approach. SGM is applied to both single determinant ΔSCF and spin-purified restricted open-shell Kohn-Sham (ROKS) approaches to study the accuracy of orbital optimized DFT excited states. It is found that SGM can converge challenging states where the maximum overlap method (MOM) or analogues either collapse to the ground state or fail to converge. We also report that ΔSCF/ROKS predict highly accurate excitation energies for doubly excited states (which are inaccessible via TDDFT). Singly excited states obtained via ROKS are also found to be quite accurate, especially for Rydberg states that frustrate (semi)local TDDFT. Our results suggest that orbital optimized excited state DFT methods can be used to push past the limitations of TDDFT to doubly excited, charge-transfer, or Rydberg states, making them a useful tool for the practical quantum chemist's toolbox for studying excited states in large systems.

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

Valence shell electronically excited states of norbornadiene and quadricyclane

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C 7 H 8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 1 1 B 1 –1 1 A 1 (3sa 1 ← 5b 1 ) band and that predicted by Franck–Condon and Herzberg–Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b 2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ~5.4 and 7.0 eV.

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

Photoabsorption, photoionization, and Auger processes at the carbon K edge in C H 3 I

The dynamics of photoabsorption, photoionization, and the associated Auger decay have been investigated at the carbon K edge in methyl iodide (CH 3 I) using linearly polarized synchrotron radiation. Ion yield measurements were used to investigate transitions in the pre-edge region due to excitations into either unoccupied valence or Rydberg states. The assignment of these transitions was achieved through comparison with theoretical x-ray absorption spectra calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation. Several of the Rydberg states belonging to series converging onto the C1s ionization limit exhibit significant vibrational structure that is also interpreted using theoretical calculations. The C1s in CH 3 I photoelectron spectrum was measured, and the observed vibrational structure was assigned with the aid of theoretical predictions. Polarization dependent, resonantly excited, valence shell photoelectron spectra were recorded at photon energies coinciding with the C1s → σ*, C1s → 6sa1 and C1s → 6pe transitions in CH 3 I , thereby allowing photoelectron angular distributions to be determined. The nonresonantly excited C(KVV) Auger electron spectrum was measured and some of the features observed at high kinetic energies were attributed to transitions into valence orbitals possessing significant iodine character. The contributions of participator and spectator Auger decay to the resonantly excited photoelectron spectra have been assessed. The influence of participator decay appears minor whereas spectator decay results in the enhanced population of satellite states.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Electron beam characterization via quantum coherent electric field imaging

We demonstrate an all-optical, minimally invasive electron beam (𝑒−beam) characterization using Rydberg electrometry. An 𝑒-beam passes through a localized detector volume containing thermal Rb atoms that are optically excited in a quantum superposition of ground and Rydberg states. The 𝑒-beam's electric field perturbs atomic coherence and modifies resonance fluorescence in a narrow spectral region near the two-photon optical transition. Imaging Rb fluorescence provides a map of the electric field from the 𝑒-beam via Rydberg state Stark shifts and allows us to reconstruct the 𝑒-beam width, centroid position, and current. For an 𝑒-beam of 20 keV and electron currents of 20–40 µ⁢A, we measured the centroid position with an accuracy of ≤ 8 µ⁢m and width to within 100 µ⁢m, limited by the experimental sensitivity of electric field reconstruction of ∼0.02 V/cm. This method is suitable for a wide range of electron energies and currents, and can be adopted for nuclear and high-energy experiments for minimally invasive real-time diagnostics and profiling of charged particle beams.

Behary, Rob [College of William and Mary, Williams↗
DOE OSTI2021

Observation of a dipole-bound excited state in 4-ethynylphenoxide and comparison with the quadrupole-bound excited state in the isoelectronic 4-cyanophenoxide

Negative ions do not possess Rydberg states, but can have Rydberg-like nonvalence excited states near the electron detachment threshold, including dipole-bound states (DBSs) and quadrupole-bound states (QBSs). While DBSs have been studied extensively, quadrupole-bound excited states have been more rarely observed. 4-cyanophenoxide (4CP – ) was the first anion observed to possess a quadrupole-bound exited state 20 cm-1 below its detachment threshold. Here we report the observation of a DBS in the isoelectronic 4-ethynylphenoxide anion (4EP – ), providing a rare opportunity to compare the behaviors of a dipole-bound and a quadrupole-bound excited state in a pair of very similar anions. Photodetachment spectroscopy (PDS) of cryogenically-cooled 4EP – reveals a DBS 76 cm -1 below its detachment threshold. Photoelectron spectroscopy (PES) at 266 nm shows that the electronic structure of 4EP – and 4CP – are nearly identical. The observed vibrational features in both the PDS and PES, as well as autodetachment from the nonvalence excited states, are also found to be similar for both anions. However, resonant two-photon detachment (R2PD) from the bound vibrational ground state is observed to be very different for the DBS in 4EP – and the QBS in 4CP – . The R2PD spectra reveal that decays take place from both the DBS and QBS to the respective anion ground electronic states within the 5 ns detachment laser pulse due to internal conversion followed by intramolecular vibrational redistribution (IVR), but the decay mechanisms appear to be very different. In the R2PD spectrum of 4EP – , we observe strong threshold electron signals, which are due to detachment, by the second photon, of highly rotationally excited anions resulted from the decay of the DBS. On the other hand, in the R2PD spectrum of 4CP – we observe well-resolved vibrational peaks due to the three lowest-frequency vibrational modes of 4CP – , which are populated from the decay of the QBS. Here, the different behaviors of the R2PD spectra suggest unexpected differences between the relaxation mechanisms of the dipole-bound and quadrupole-bound excited states.

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

Sum of oscillator-strength moments and asymptotic behaviour of thermally induced broadening and shift of energy levels of Rydberg atom circular states

Based on the rules for summing oscillator-strength moments, we derive analytical expressions for environmentally (thermally) induced energy-level shifts and broadenings of circular Rydberg states with maximum orbital (l) and magnetic (m) quantum numbers, l = |m| = n – 1. The formulae for the energy of interaction with blackbody radiation are presented in the form of series expansion in even powers of the small parameter η = Z{sup 2}/(n{sup 3}k{sub B}T) ≪ 1 in the region of high temperatures T and principal quantum numbers n (Z is the charge of the residual ion). The expression for the thermally induced width contains a negative temperature-independent term coinciding in absolute value with the spontaneous width, so that the temperature-independent term is absent in the expression for the sum of the spontaneous and thermally induced widths. A similar expansion in powers of η for the thermally induced shift also contains a temperature-independent term proportional to 1/n{sup 6}. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Distinguishing resonance symmetries with energy-resolved photoion angular distributions from ion-pair formation in O 2 following two-photon absorption of a 9.3 eV femtosecond pulse

We present a combined experimental and theoretical study on the photodissociation dynamics of ion-pair formation in O 2 following resonant two-photon absorption of a 9.3 eV femtosecond pulse, where the resulting O + ions are detected using 3-D momentum imaging. Ion-pair formation states of $^3\Sigma^-_g$ and $^3\Pi_g$ symmetry are accessed through predissociation of optically dark continuum Rydberg states converging to the B $^2\Sigma^-_g$ ionic state, which are resonantly populated via a mixture of both parallel-parallel and parallel-perpendicular two-photon transitions. This mixture is evident in the angular distribution of the dissociation relative to the light polarization, and varies with the kinetic energy release (KER) of the fragmenting ion-pair. The KER-dependent photoion angular distribution reveals the underlying two-photon absorption dynamics involved in the ion-pair production mechanism and indicates the existence of two nearly degenerate continuum resonances possessing different symmetries, which can both decay by coupling to ion-pair states of the same total symmetry through internal conversion.

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

Fast Preparation and Detection of a Rydberg Qubit Using Atomic Ensembles

Here, we demonstrate a new approach for fast preparation, manipulation, and collective readout of an atomic Rydberg-state qubit. By making use of Rydberg blockade inside a small atomic ensemble, we prepare a single qubit within 3 μs with a success probability of $F_p$ = 0.93 ± 0.02, rotate it, and read out its state in 6 μs with a single-shot fidelity of $F_d$ = 0.92 ± 0.04. The ensemble-assisted detection is 10 3 times faster than imaging of a single atom with the same optical resolution, and enables fast repeated nondestructive measurement. We observe qubit coherence times of 15 μs, much longer than the π rotation time of 90 ns. Potential applications ranging from faster quantum information processing in atom arrays to efficient implementation of quantum error correction are discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Hybridization of Excited Interlayer Excitons with Intralayer Excitons in Transition-Metal Dichalcogenide Heterostructures: Interplay of Orbital and Structural Symmetry

Hybridization between interlayer exciton (ILX) and intralayer excitons offers a powerful route to engineer light–matter interactions in transition-metal dichalcogenide (TMDC) heterostructures, yet the underlying mechanism and selection rules remain elusive. Here we probe exciton hybridization in MoTe2/MoSe2 heterobilayers under a tunable out-of-plane electric field and observe distinct avoided crossings in the electric-field dependent reflection spectra. We associate them with coupling between excited ILX states, including the 2p and 2s Rydberg states, and MoTe2 intralayer exciton. Supported by ab initio GW plus Bethe-Salpeter equation (GW-BSE) calculations, we identify the hybridizing states and establish optical selection rules based on the effective angular momentum of the exciton states. These findings highlight the role of excitonic binding in the observed hybridization, rather than that of simple band-mixing models, and provide a new pathway for brightening high-energy dark states.

Yao, Helen [Department of Materials Science and En↗
DOE OSTI2021

Two-photon above-threshold ionization of helium

Multiphoton ionization provides a clear window into the nature of electron correlations in the helium atom. In the present study, the final-state energy range extends up to the region near the N = 2 and N = 3 ionization thresholds, where two-photon ionization proceeds via continuum intermediate states above the lowest threshold. Our calculations are performed using multichannel quantum defect theory (MQDT) and the streamlined R-matrix method. The sum and integration over all intermediate states in the two-photon ionization amplitude is evaluated using the inhomogeneous R-matrix method developed by Robicheaux and Gao. The seamless connection of that method with MQDT allows us to present high-resolution spectra of the final-state Rydberg resonances. Our analysis classifies the resonances above the N = 2 threshold in terms of their group theory quantum numbers. Furthermore, their dominant decay channels are found to obey the previously conjectured propensity rule far more weakly for these even-parity states than was observed for the odd-parity states relevant to single-photon ionization.

74 ATOMIC AND MOLECULAR PHYSICS↗
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

Prediction of photodynamics of 200 nm excited cyclobutanone with linear response electronic structure and ab initio multiple spawning

Simulations of photochemical reaction dynamics have been a challenge to the theoretical chemistry community for some time. In an effort to determine the predictive character of current approaches, we predict the results of an upcoming ultrafast diffraction experiment on the photodynamics of cyclobutanone after excitation to the lowest lying Rydberg state (S 2 ). A picosecond of nonadiabatic dynamics is described with ab initio multiple spawning. Herein we use both time dependent density functional theory (TDDFT) and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) theory for the underlying electronic structure theory. We find that the lifetime of the S 2 state is more than a picosecond (with both TDDFT and EOM-CCSD). The predicted ultrafast electron diffraction spectrum exhibits numerous structural features, but weak time dependence over the course of the simulations.

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

A dual-species Rydberg array

Large-scale Rydberg atom arrays are used for highly coherent analogue quantum simulations and for digital quantum computations. However, advanced quantum protocols, such as quantum error correction, require midcircuit qubit operations, including the replenishment, reset and read-out of a subset of qubits. A compelling strategy for unlocking these capabilities is a dual-species architecture in which a second atomic species is controlled independently and entangled with the first through Rydberg interactions. Here, we realize a dual-species Rydberg array consisting of rubidium and caesium atoms and explore regimes of interactions and dynamics not accessible in single-species architectures. We achieve enhanced interspecies interactions by electrically tuning the Rydberg states close to a Förster resonance. In this regime, we demonstrate an interspecies Rydberg blockade and implement a quantum state transfer from one species to another. We then generate a Bell state between Rb and Cs hyperfine qubits through an interspecies controlled-phase gate. Finally, we combine interspecies entanglement with a native midcircuit read-out to achieve quantum non-demolition measurements.

atomic and molecular interactions with photons↗