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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Autoionization dynamics of ( 2 P 1/2 ) ns/d states in krypton probed by noncollinear wave mixing with attosecond extreme ultraviolet and few-cycle near infrared pulses

The autoionization dynamics of the ( 2 P 1/2 )ns/d Rydberg states in krypton are investigated using spatially isolated wave-mixing signals generated with a short train of subfemtosecond extreme ultraviolet (XUV) pulses and noncollinear, few-cycle near infrared pulses. Despite ubiquitous quantum beat oscillations from XUV-induced coherences within the excited-state manifold, these wave-mixing spectra allow for the simultaneous evaluation of autoionization lifetimes from a series of Rydberg states above the first ionization potential. Experimentally measured lifetimes of 22 ± 8 fs, 33 ± 6 fs, and 49 ± 6 fs for the wave-mixing signals emitting from the ( 2 P 1/2 )6d/8s, ( 2 P 1/2 )7d/9s, and ( 2 P 1/2 )8d/10s resonances compare favorably with lifetimes for the ( 2 P 1/2 )6d, 7d, and 8d Rydberg states determined from spectral linewidths. Analysis of the quantum beats reveals that the enhancement of wave-mixing pathways that couple the ( 2 P 1/2 )nd states to themselves leads to individual reporter state-dependent decays in the wave-mixing signals. Lastly, the results demonstrate the promise of wave-mixing spectroscopies with subfemtosecond XUV pulses to provide valuable insights into processes governed by electronic dynamics.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger molecules.

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

Interpretation of the vacuum ultraviolet photoabsorption spectrum of iodobenzene by ab initio computations

Identification of many Rydberg states in iodobenzene, especially from the first and fourth ionization energies (IE{sub 1} and IE{sub 4}, X{sup 2}B{sub 1} and C{sup 2}B{sub 1}), has become possible using a new ultraviolet (UV) and vacuum-ultraviolet (VUV) absorption spectrum, in the region 29 000-87 000 cm{sup −1} (3.60-10.79 eV), measured at room temperature with synchrotron radiation. A few Rydberg states based on IE{sub 2} (A{sup 2}A{sub 2}) were found, but those based on IE{sub 3} (B{sup 2}B{sub 2}) are undetectable. The almost complete absence of observable Rydberg states relating to IE{sub 2} and IE{sub 3} (A{sup 2}A{sub 2} and B{sup 2}B{sub 2}, respectively) is attributed to them being coupled to the near-continuum, high-energy region of Rydberg series converging on IE{sub 1}. Theoretical studies of the UV and VUV spectra used both time-dependent density functional (TDDFT) and multi-reference multi-root doubles and singles-configuration interaction methods. The theoretical adiabatic excitation energies, and their corresponding vibrational profiles, gave a satisfactory interpretation of the experimental results. The calculations indicate that the UV onset contains both 1{sup 1}B{sub 1} and 1{sup 1}B{sub 2} states with very low oscillator strength, while the 2{sup 1}B{sub 1} state was found to lie under the lowest ππ{sup ∗} 1{sup 1}A{sub 1} state. All three of these {sup 1}B{sub 1} and {sup 1}B{sub 2} states are excitations into low-lying σ{sup ∗} orbitals. The strongest VUV band near 7 eV contains two very strong ππ{sup ∗} valence states, together with other weak contributors. The lowest Rydberg 4b{sub 1}6s state (3{sup 1}B{sub 1}) is very evident as a sharp multiplet near 6 eV; its position and vibrational structure are well reproduced by the TDDFT results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Population transfer in the Na s-p Rydberg ladder by a chirped microwave pulse

While quantum defects of nl Rydberg states of Na with l{>=}2 are nearly equal to zero, the quantum defects of ns and np states of Na are quite large due to the finite size of its ionic core. Since the Na ns and np states are energetically isolated from the higher angular momentum states of the same n, we can think of the Na ns and np Rydberg states as a specific example of a simple multilevel ladder system consisting of only alternating s and p angular momentum states. Here we report that population transfer in the Na s-p Rydberg ladder can be effectively achieved using a frequency-chirped microwave pulse, which couples only s and p states under suitable conditions.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1994

Supersymmetry and radial squeezed states for Rydberg wave packets

Atomic supersymmetry provides an analytical effective-potential model useful for describing certain aspects of Rydberg atoms. Experiments have recently demonstrated the existence of Rydberg wave packets localized in the radial coordinated with p-state angular distribution. This paper shows how atomic supersymmetry can be used to treat radial Rydberg wave packets via a particular analytical type of squeezed state, called a radial squeezed state.

Bluhm, Robert↗
DOE OSTI2011

High-order harmonic generation with Rydberg atoms by using an intense few-cycle pulse

We demonstrate that high-order harmonic generation (HHG) with both high cutoff frequency and high conversion efficiency can be realized by using a Rydberg atom in a few-cycle laser pulse. This is because a Rydberg state has a large electron orbital radius and small binding energy; therefore an electron in the Rydberg state can be ionized easily and accelerated directly toward the core under the interaction of a few-cycle laser pulse, leading to emission of harmonic photons. In this case, the tunneling process of the electron is not involved and, hence, the conversion efficiency and the cutoff frequency of harmonic generation can be higher than that predicted by the conventional three-step model.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Scheme of a hydrogen-molecule quantum simulator based on two ultracold rubidium atoms

A scheme is proposed for implementing a hydrogen-molecule quantum simulator based on two ultracold rubidium atoms trapped into spatially separated optical dipole traps. The scheme includes the adiabatic preparation of the initial quantum state of two atoms and the iterative quantum phase estimation. The accuracy of measuring the ground state energy of a molecule is numerically calculated as a function of the number of iterations. The simulation is performed using two-qubit gates based on the dipole blockade effect under short-term excitation of atoms into the Rydberg states with allowance for the finite lifetime of Rydberg states and the finite energies of the van der Waals interaction. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
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 OSTI2014

Sub-wavelength imaging and field mapping via electromagnetically induced transparency and Autler-Townes splitting in Rydberg atoms

We present a technique for measuring radio-frequency (RF) electric field strengths with sub-wavelength resolution. We use Rydberg states of rubidium atoms to probe the RF field. The RF field causes an energy splitting of the Rydberg states via the Autler-Townes effect, and we detect the splitting via electromagnetically induced transparency (EIT). We use this technique to measure the electric field distribution inside a glass cylinder with applied RF fields at 17.04 GHz and 104.77 GHz. We achieve a spatial resolution of ≈100 μm, limited by the widths of the laser beams utilized for the EIT spectroscopy. We numerically simulate the fields in the glass cylinder and find good agreement with the measured fields. Our results suggest that this technique could be applied to image fields on a small spatial scale over a large range of frequencies, up into the sub-terahertz regime.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Vibrational autoionization of state-selective jet-cooled methanethiol (CH 3 SH) investigated with infrared + vacuum-ultraviolet photoionization

Vibrational autoionization of Rydberg states provides key information about nonadiabatic processes above an ionization threshold. In this work, we employed time-of-flight mass detection of CH 3 SH + to record vibrational-state selective photo-ionization efficiency (PIE) spectra of jet-cooled methanethiol (CH 3 SH) on exciting CH 3 SH to a specific vibrationally excited state with an infrared (IR) laser, followed by excitation with a tunable laser in the vacuum-ultraviolet (VUV) region for ionization. Autoionizing Rydberg states assigned to the ns, np, nd and nf series are identified. When IR light at 2601 (ν 3 , SH stretching mode) and 2948 cm -1 (ν 2 , CH 3 symmetric stretching mode) was employed, the Rydberg series converged to the respective vibrationally excited (ν 3 and ν 2 ) states of CH 3 SH + . When IR light at 3014 cm -1 (overlapped ν 1 /ν 9 , CH 3 antisymmetric stretching and CH 2 antisymmetric stretching modes) was employed, Rydberg series converging to two vibrationally excited states (ν 1 and ν 9 ) of CH 3 SH + were observed. When IR light at 2867 cm -1 (2ν 10 , overtone of CH 3 deformation mode) and 2892 cm -1 (2ν 4 , overtone of CH 2 scissoring mode) was employed, both Δν = -1 and Δν = -2 ionization transitions were observed; there is evidence for direct ionization from the initial state into the CH 3 SH + (ν 4 + = 1) continuum. In all observed IR-VUV-PIE spectra, the ns and nd series show intensity greater than the other Rydberg series, which is consistent with the fact that the highest-occupied molecular orbital of CH 3 SH is a p-like lone pair orbital on the S atom. Finally, the quantum yields for autoionization of various vibrational excited states are discussed. Values of ν 1 = 3035, ν 2 = 2884, ν 3 = 2514, and ν 9 = 2936 cm -1 for CH 3 SH + derived from the converged limits agree satisfactorily with values observed for Ar-tagged CH 3 SH + at 3026, 2879, 2502, and 2933 cm -1 .

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

Spectral dependence of photoemission in multiphoton ionization of NO 2 by femtosecond pulses in the 375–430 nm range

In this paper, we investigate the multiphoton ionization of NO 2 using tunable (430–375 nm) femtosecond pulses and photoelectron–photoion coincidence momentum spectroscopy. In order to understand the complex electronic and nuclear photodynamics at play following absorption of three to five photons, we also report extended photoionization calculations using correlated targets and coupled channels. Exploring the multiphoton dissociative ionization (MPDI) and multiphoton ionization (MPI) processes over such a broad energy range enables us to lend further support to our work carried out around 400 nm of a femtosecond laser [S. Marggi Poullain et al., J. Phys. B: At., Mol. Opt. Phys., 2014, 47, 124024]. Two excitation energy regions are identified and discussed in terms of the proposed reaction pathways, highlighting the significant role of Rydberg states, such as the [R*(6a 1 ) -1 , 3pσ] Rydberg state, in the NO 2 multiphoton excitation and photoionization. These new results support our previous assumption that different bent and linear geometries of the NO 2 + (X 1 Σ g ) ionic state contribute to the MPDI and MPI, consistent with the reported calculations which reveal an important vibronic coupling characterizing the photoemission. Finally, remarkably, the strong anisotropy of the recoil frame photoelectron angular distribution (RFPAD) previously observed at 400 nm appears as a fingerprint across the whole explored photon energy range.

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

Synchrotron-based valence shell photoionization of CH radical

We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Autoionization states of SO2

Assignments are reported for the autoionizing states of SO2(+) in the 1020-630 A region. The Rydberg states of SO(+) were observed by the method of molecular beam photoionization mass spectrometry, which ensures that all the states observed are autoionizing in nature. The vibrational progressions obtained are assigned to the 4b2-3s, 4b2-3d, 7a1-3p, 7a1-3d, and 2b1-3p Rydberg states. Dips in the photoionization efficiency curves of SO2(+) and SO(+) correspond to those of a window resonance series previously observed in photoabsorption.

Wu, C. Y. R.↗
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 OSTI2014

Influence of magnetic field on laser-produced barium plasmas: Spectral and dynamic behaviour of neutral and ionic species

The expansion dynamics and spectral behaviour of plasma produced by a Nd:YAG laser (λ=1.064 μm, pulse width: 8 ns) from barium target and expanding in 0.45 T transverse magnetic field in vacuum (10⁻⁵Torr pressure) are investigated using time-of-flight optical emission spectroscopy. The experiments are carried out at various laser fluences from 12 to 31 J/cm². The temporal profiles of neutral (Ba I 553.5 and 577.7 nm) lines are temporally broadened, while that of ionic (Ba II 413.0 and 455.4 nm) lines show strong confinement in the presence of a magnetic field. In the absence of magnetic field, the temporal profile of Ba I 553.5 nm is exactly reproduced by fitting with two Shifted Maxwell Boltzmann (SMB) Distribution components, while in the presence of a magnetic field the profile could only be fitted with three components. The field enhanced and field induced SMB components of neutral profile are correlated with populations of ground state, metastable states, and long-lived Rydberg states present in the barium plasma, while SMB components of ionic lines are explained on the basis of the presence of super-elastic collisions among the excited species in the plasma. The spatial variation of electron temperature and temporal variation of electron density are deduced and correlated to the different collisional processes in the barium plasma. The ionic profiles show efficient confinement in the presence of a magnetic field at higher fluences.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
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 OSTI2011

Xe{sup +} formation following photolysis of Au-Xe: A velocity map imaging study

The photodissociation dynamics of Au-Xe leading to Xe{sup +} formation via the {Xi}{sub 1/2}-X{sup 2}{Sigma}{sup +} (v{sup '}, 0) band system (41 500-41 800 cm{sup -1}) have been investigated by velocity map imaging. Five product channels have been indentified, which can be assigned to photoinduced charge transfer followed by photodissociation in either the neutral or the [Au-Xe]{sup +} species. For the neutral species, charge transfer occurs via a superexcited Rydberg state prior to dissociative ionization, while single-photon excitation of the gold atom in Au{sup +}-Xe accesses an (Au{sup +})*-Xe excited state that couples to a dissociative continuum in Au-Xe{sup +}. Mechanisms by which charge transfer occurs are proposed, and branching ratios for Xe{sup +} formation via the superexcited Rydberg state are reported. The bond dissociation energy for the first excited state of Au{sup +}-Xe is determined to be {approx}9720 {+-} 110 cm{sup -1}.

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