Ultrafast relaxation of photoexcited superfluid He nanodroplets

The relaxation of photoexcited nanosystems is a fundamental process of light-matter interaction. Depending on the couplings of the internal degrees of freedom, relaxation can be ultrafast, converting electronic energy in a few fs, or slow, if the energy is trapped in a metastable state that decouples from its environment. Here, we study helium nanodroplets excited resonantly by femtosecond extreme-ultraviolet (XUV) pulses from a seeded free- electron laser. Despite their superfluid nature, we find that helium nanodroplets in the lowest electronically excited states undergo ultrafast relaxation. By comparing experimental pho- toelectron spectra with time-dependent density functional theory simulations, we unravel the full relaxation pathway: Following an ultrafast interband transition, a void nanometer-sized bubble forms around the localized excitation (He ) within 1 ps. Subsequently, the bubble collapses and releases metastable He at the droplet surface. This study highlights the high level of detail achievable in probing the photodynamics of nanosystems using tunable XUV pulses

Soft Chemical Control of Superconductivity in Lithium Iron Selenide Hydroxides Li1–x_{1–x}Fex_x(OH)Fe1–y_{1–y}Se

Hydrothermal synthesis is described of layered lithium iron selenide hydroxides Li$_{1–x}$Fex(OH)Fe$_{1–y}$Se (x$\sim$0.2; 0.02 < $y$ < 0.15) with a wide range of iron site vacancy concentrations in the iron selenide layers. This iron vacancy concentration is revealed as the only significant compositional variable and as the key parameter controlling the crystal structure and the electronic properties. Single crystal X-ray diffraction, neutron powder diffraction, and X-ray absorption spectroscopy measurements are used to demonstrate that superconductivity at temperatures as high as 40 K is observed in the hydrothermally synthesized samples when the iron vacancy concentration is low ($y$ < 0.05) and when the iron oxidation state is reduced slightly below +2, while samples with a higher vacancy concentration and a correspondingly higher iron oxidation state are not superconducting. The importance of combining a low iron oxidation state with a low vacancy concentration in the iron selenide layers is emphasized by the demonstration that reductive postsynthetic lithiation of the samples turns on superconductivity with critical temperatures exceeding 40 K by displacing iron atoms from the Li$_{1–x}$Fe$_x$(OH) reservoir layer to fill vacancies in the selenide layer

PROBING THE STRUCTURE OF IONIC LIQUID SURFACES BY ROTATIONALLY AND ELECTRONICALLY INELASTIC SCATTERING OF NO

Author Institution: JILA, University of Colorado and National Institute of Standards and Technology, Boulder, Colorado, USARoom temperature ionic liquids (RTIL's) are a highly diverse class of materials with many potential technological applications. They are candidates for use in advanced electrolytes, green solvents, and supported liquid membranes for CO$_2$ sequestration. We present studies where inelastic scattering of high or low velocity nitric oxide provides insight into the microscopic structure of these complex surfaces. As an open shell diatomic, jet-cooled NO [$^2\Pi_{1/2}$(J = 0.5)] features both molecular and electronic collision dynamics as seen by probing scattered rotational and spin-orbit distributions respectively. These studies show substantial variation in degree of rotational and electronic excitation as ionic liquid identity is varied. Also, surface heating is found to have a strong effect on scattered spin-orbit branching, possibly due to the dependence of surface structure on temperature. This is discussed in terms of a picture where the electronic degree of freedom may serve as a sensitive measure of the cationic versus anionic nature of the top few layers of this material

Ultrafast relaxation of photoexcited superfluid He nanodroplets

The relaxation of photoexcited nanosystems is a fundamental process of light-matter interaction. Depending on the couplings of the internal degrees of freedom, relaxation can be ultrafast, converting electronic energy in a few fs, or slow, if the energy is trapped in a metastable state that decouples from its environment. Here, helium nanodroplets are resonantly excited by femtosecond extreme-ultraviolet (XUV) pulses from a seeded free-electron laser. Despite their superfluid nature, we find that helium nanodroplets in the lowest electronically excited states undergo ultrafast relaxation. By comparing experimental photoelectron spectra with time-dependent density functional theory simulations, we unravel the full relaxation pathway: Following an ultrafast interband transition, a void nanometer-sized bubble forms around the localized excitation (He*) within 1 ps. Subsequently, the bubble collapses and releases metastable He* at the droplet surface. This study highlights the high level of detail achievable in probing the photodynamics of nanosystems using tunable XUV pulses