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Register a new userRIXS Reveals Hidden Local Transitions of the Aqueous OH Radical
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Resonant inelastic x-ray scattering (RIXS) provides remarkable opportunities to interrogate ultrafast dynamics in liquids. Here we use RIXS to study the fundamentally and practically important hydroxyl radical in liquid water, OH(aq). Impulsive ionization of pure liquid water produced a short-lived population of OH(aq), which was probed using femtosecond x-rays from an x-ray free-electron laser. We find that RIXS reveals localized electronic transitions that are masked in the ultraviolet absorption spectrum by strong charge-transfer transitions -- thus providing a means to investigate the evolving electronic structure and reactivity of the hydroxyl radical in aqueous and heterogeneous environments. First-principles calculations provide interpretation of the main spectral features.
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We report on the observation of magnetic dipole allowed transitions in the well-characterized $A,^2Sigma^+ - X,^2Pi$ band system of the OH radical. A Stark decelerator in combination with microwave Rabi spectroscopy is used to control the populations in selected hyperfine levels of both $Lambda$-doublet components of the $X,^2Pi_{3/2},v=0,J=3/2$ ground state. Theoretical calculations presented in this paper predict that the magnetic dipole transitions in the $ u=1 leftarrow u=0$ band are weaker than the electric dipole transitions by a factor of $2.58times 10^3$ only, i.e., much less than commonly believed. Our experimental data confirm this prediction.
Transient diode laser absorption spectroscopy has been used to measure three strong vibronic bands in the near infrared spectrum of the C$_2$H, ethynyl, radical not previously observed in the gas phase. The radical was produced by ultraviolet excimer laser photolysis of either acetylene or (1,1,1)-trifluoropropyne in a slowly flowing sample of the precursor diluted in inert gas, and the spectral resolution was Doppler-limited. The character of the upper states was determined from the rotational and fine structure in the observed spectra and assigned by measurement of ground state rotational combination differences. The upper states include a $^2Sigma ^+$ state at 6696 cm$^{-1}$, a second $^2Sigma ^+$ state at 7088 cm$^{-1}$, and a $^2Pi$ state at 7110 cm$^{-1}$. By comparison with published calculations (R. Tarroni and S. Carter, textit{J. Chem. Phys} textbf{119}, 12878 (2003) and textit{Mol. Phys}. textbf{102}, 2167 (2004)), the vibronic character of these levels was also assigned. The observed states contain both $X^2Sigma^+$ and $A^2Pi$ electronic character. Several local rotational level perturbations were observed in the excited states. Kinetic measurements of the time-evolution of the ground state populations following collisional relaxation and reactive loss of the radicals formed in a hot, non-thermal, population distribution were made using some of the strong rotational lines observed. The case of C$ _{2} $H may be a good place to investigate the behavior at intermediate pressures of inert colliders, where the competition between relaxation and reaction can be tuned and observed to compare with master equation models, rather than deliberately suppressed to measure thermal rate constants.
Two-photon anti-bunching at a beamsplitter is only possible if the photons are entangled in a specific state, anti-symmetric in the spatial modes. Thus, observation of anti-bunching is an indication of entanglement in a degree of freedom which might not be easily accessible in an experiment. We experimentally demonstrate this concept in the case of the interference of two frequency entangled photons with continuous frequency detunings. The principle of anti-symmetrisation of the spatial part of a wavefunction and subsequent detection of hidden entanglement via anti-bunching at a beamsplitter may facilitate the observation of entanglement in other systems, like atomic ensembles or Bose-Einstein condensates. The analogue for fermionic systems would be to observe bunching.
Frequency-modulated diode laser transient absorption spectra of the ethynyl radical have been recorded at wavelengths close to 1.66 $mu$m. The observed spectrum includes strong, regular, line patterns. The two main bands observed originate in the ground $tilde{X},^2Sigma^+$ state and its first excited bending vibrational level of $^2Pi$ symmetry. The upper states, of $^2Sigma^+$ symmetry at 6055.6 cm$^{-1}$ and $^2Pi$ symmetry at 6413.5 cm$^{-1}$, respectively, had not previously been observed and the data were analyzed in terms of an effective Hamiltonian representing their rotational and fine structure levels to derive parameters which can be used to calculate rotational levels up to J = 37/2 for the $^2Pi$ level and J = 29/2 for the $^2Sigma$ one. Additionally, a weaker series of lines have been assigned to absorption from the second excited bending, (020), level of $^2Sigma$ symmetry, to a previously observed state of $^2Pi$ symmetry near 6819 cm$^{-1}$. These strong absorption bands at convenient near-IR laser wavelengths will be useful for monitoring CCH radicals in chemical systems.
SS433 is the only Galactic binary system known to persistently accrete at highly super-critical (or hyper-critical) rates, similar to those in tidal disruption events, and likely needed to explain the rapid growth of those very high redshift quasars containing massive SMBHs. Probing the inner regions of SS433 in the X-rays is crucial to understanding this system, and super-critical accretion in general, but is highly challenging due to obscuration by the surrounding wind, driven from the accretion flow. NuSTAR observed SS433 in the hard X-ray band across multiple phases of its 162 day super-orbital precession period. Spectral-timing tools allow us to infer that the hard X-ray emission from the inner regions is likely being scattered towards us by the walls of the wind-cone. By comparing to numerical models, we determine an intrinsic X-ray luminosity of $ge$ 2$times$10$^{37}$ erg/s and that, if viewed face on, we would infer an apparent luminosity of $>$ 1$times$10$^{39}$ erg/s, confirming SS433s long-suspected nature as an ultraluminous X-ray source (ULX). We present the discovery of a narrow, $sim 100$s lag due to atomic processes occurring in outflowing material travelling at least 0.14-0.29c, which matches absorption lines seen in ULXs and -- in the future -- will allow us to map a super-critical outflow for the first time.
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