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K(BH)6 crystallizes in the cubic Fm-3 space group. The structure is three-dimensional. K is bonded in a distorted q6 geometry to twelve equivalent H atoms. All K–H bond lengths are 2.95 Å. B is bonded in a single-bond geometry to one H atom. The B–H bond length is 1.20 Å. H is bonded in a single-bond geometry to two equivalent K and one B atom.
Here, the crystal structures of CaB – Hn compounds with n = 1 – 12 in a pressure range of 50–300 GPa were studied using the genetic algorithm method and first-principles density-function theory calculations. Stable structures with stoichiometry of CaB H 6 and CaB H 7 were predicted in different pressure range. BH 4 , BH 5 , and BH 6 units were found to be the main motifs in these compounds. Moreover, metastable Imm2 CaB H 7 is dynamically stable above 180 GPa, with the formation of tetrahedral BH 4 unit surrounded by Ca atom and H 3 unit. Electron-phonon coupling (EPC) calculations reveal that the superconducting properties are closely related to the strong hydrogen-boron bonding of the BH 4 unit in Imm2, and T c can reach ~200 K at 200 GPa. As the major units, BH 4 , BH 5 , and BH 6 units exist in the Imm2, P 2 , and P2 1 /m phases of CaB H 7 at 300 GPa, respectively; the corresponding EPC parameter λ decreases with the increase of hydrogen content in CaB H 7 .
σ-Hydrocarbyl complexes of the form [M(η 5 -PC 4 Me 4 ) 2 (μ-η 1 :η 6 -CH 2 Ph) 2 K(η 6 -arene)] (M = La, Ce, Pr, U, Np, Pu; arene = benzene or toluene) were synthesised in one-pot reactions from [MI 3 (THF) 4 ], or [U(BH 4 ) 3 (toluene)] (M = U). All complexes were examined by multinuclear ( 1 H, 13 C{ 1 H}, 31 P{ 1 H}) NMR and UV-vis-NIR spectroscopy, as well as single-crystal X-ray diffraction from which molecular metal–phosphorus bonds for Np and Pu, and a σ-hydrocarbyl metal–carbon bond for Pu, have been structurally authenticated.
Metal borohydride complexes have long been the subject of intense fundamental interest because of their unconventional metal–ligand bonding that occurs via three-center, two-electron M–H–B bonds. This type of bonding implies significant delocalization of electron density over all three atoms, but the degree of orbital mixing between the metal and boron has been difficult to assess by direct experimental means. Herein, we demonstrate how ligand K-edge X-ray absorption spectroscopy (XAS) conducted at the B K-edge yields evidence of significant covalent M–H–B bonding with Zr and Hf. To accommodate the B K-edge XAS studies, which were conducted under ultra-high vacuum (<10 −8 torr), we prepared a series of new [Zr(RBH 3 ) 4 ] and [Hf(RBH 3 ) 4 ] complexes with substituents that attenuate volatility (R = benzyl, phenyl, mesityl, 2,4,6-triisopropylphenyl, and anthryl). 1 H and 11 B NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction (XRD) studies revealed metal and ligand dependent differences in the BH 3 chemical shifts that correlate to changes in M−B distances and select B–H vibrational stretching modes. The B K-edge XAS spectra of the Zr and Hf complexes yielded a pre-edge feature that was assigned as B 1s → M–H–B π* based on comparison to time-dependent density functional theory (TDDFT) calculations. The pre-edge transitions appear due to covalent mixing between boron and the metal, thereby demonstrating how B K-edge XAS can provide direct evidence of covalent three-center, two electron M–H–B bonding in borohydride complexes using boron as a spectroscopic reporter.
A possible accretion model associated with the ionization instability of quasar disks is proposed to address the growth of the central black hole (BH) harbored in the host galaxy. The evolution of quasars in cosmic time is assumed to change from a highly active state to a quiescent state triggered by the S-shaped ionization instability of the quasar accretion disk. For a given external mass transfer rate supplied by the quasar host galaxy, ionization instability can modify the accretion rate in the disk and separate the accretion flows of the disk into three different phases, like an S-shape. We suggest that the bright quasars observed today are those quasars with disks in the upper branch of the S-shaped instability, and the faint or 'dormant' quasars are simply these systems in the lower branch. The middle branch is the transition state, which is unstable. We assume the quasar disk evolves according to the advection-dominated inflow-outflow solution (ADIOS) configuration in the stable lower branch of the S-shaped instability, and the Eddington accretion rate is used to constrain the accretion rate in the highly active phase. The mass ratio between a BH and its host galactic bulge is a natural consequence of an ADIOS. Our model also demonstrates that a seed BH approx. 2 x 10(exp 6) solar masses similar to those found in spiral galaxies today is needed to produce a BH with a final mass of approx. 2 x 10(exp 8) solar masses.
Abstract A dinuclear hafnium complex containing the parent imido ligand [(PN)(PNC)Hf=NH{μ 2 ‐K}] 2 ( 2 ) (PN − =(N‐(2‐P i Pr 2 ‐4‐methylphenyl)‐2,4,6‐Me 3 C 6 H 2 ; PNC 2− =(N‐(2‐P i Pr 2 ‐4‐methylphenyl)‐2,4,6‐CH 2 Me 2 C 6 H 2 ), was prepared by reduction of the bisazide trans‐[(PN) 2 Hf(N 3 ) 2 ] ( 1 ) with two equiv of KC 8 . Encapsulation of K + in 2 with crown‐ether or cryptand affords the first discrete salt [K(encap)][(PN)(PNC)Hf≡NH] (encap=18‐crown‐6(THF) 2 , 3 ; 2,2,2‐Kryptofix, 4 ), featuring a terminal parent imide and possessing some of the shortest Hf−N bond lengths known to date. DFT calculations revealed formation of 2 to proceed via an extremely basic monomeric nitrido, [(PN) 2 Hf≡N] − ( A ), having a computed p K BH+ of ∼57 followed by heterolytic splitting of an inert 1,2‐CH bond of a benzylic methyl group across the Hf≡N triple bond in A . An electronic structure analysis reveals A to possess a covalent Hf≡N triple bond and of super‐basic character. We also showcase reactivity of the Hf≡NH bond with various electrophiles.
In this study, a series of iridium hydride complexes featuring dihydrogen bonding are presented and shown to undergo rapid H + /H - exchange (1240 s -1 at 25 °C). We demonstrate that the H + /H - exchange rate can be modified by post-synthetic modification at a remote site using BH 3 , Zn(C 6 F 5 ) 2 , and [Me 3 O][BF 4 ]. This route provides a complementary strategy to traditional methods that rely on pre-metalation modifications to a metal's primary sphere.
By combining complementary monitoring observations spanning long, medium and short time scales, we have constructed power spectral densities (PSDs) of six Seyfert 1 galaxies. These PSDs span approx. greater than 4 orders of magnitude in temporal frequency, sampling variations on time scales ranging from tens of minutes to over a year. In at least four cases, the PSD shows a "break," a significant departure from a power law, typically on time scales of order a few days. This is similar to the behavior of Galactic X-ray binaries (XRBs), lower mass compact systems with breaks on time scales of seconds. NGC 3783 shows tentative evidence for a doubly-broken power law, a feature that until now has only been seen in the (much better-defined) PSDs of low-state XRBs. It is also interesting that (when one previously-observed object is added to make a small sample of seven), an apparently significant correlation is seen between the break time scale T and the putative black hole mass M(sub BH), while none is seen between break time scale and luminosity. The data are consistent with the linear relation T = M(sub BH) /10(exp 6.5) solar mass; extrapolation over 6-7 orders of magnitude is in reasonable agreement with XRBs. All of this strengthens the case for a physical similarity between Seyfert 1s and XRBs.
Following the discovery of high-temperature superconductivity in the La–H system, we studied the formation of new chemical compounds in the barium-hydrogen system at pressures from 75 to 173 GPa. Using in situ generation of hydrogen from NH 3 BH 3 , we synthesized previously unknown superhydride BaH 12 with a pseudocubic (fcc) Ba sublattice in four independent experiments. Density functional theory calculations indicate close agreement between the theoretical and experimental equations of state. In addition, we identified previously known P6/mmm-BaH 2 and possibly BaH 10 and BaH 6 as impurities in the samples. Ab initio calculations show that newly discovered semimetallic BaH 12 contains H 2 and H 3 – molecular units and detached H 12 chains which are formed as a result of a Peierls-type distortion of the cubic cage structure. Barium dodecahydride is a unique molecular hydride with metallic conductivity that demonstrates the superconducting transition around 20 K at 140 GPa.
Manganese is perhaps the most electronically versatile element, yet the redox properties, reactivity, and catalytic applications of low-valent Mn 0 /Mn −I complexes remain underexplored due to the propensity for Mn 0 to dimerize, quenching highenergy metalloradicals. We report a series of redox-active monometallic Mn I , Mn 0 and Mn −I complexes containing a BH 2 - bridged dicarbene, characterized using a suite of experimental and cutting-edge computational (DFT) methods. Slow electron transfer kinetics at Mn I/0 are observed, with computations and electrochemical simulations in excellent agreement with experimental values. Despite the lack of steric bulk at the BH 2 -bridged Mn 0 , the t Bu groups at the dicarbene provide adequate steric protection to prevent dimerization, with percent buried volume (% V bur ) serving as a valuable steric ranking tool. We also show that a %V bur > 83% prevents dimerization for a diverse array of Mn 0 complexes from the literature. Ligand sterics of BPh 2 -and BH 2 -bridged complexes dictate reaction outcomes when Mn I and Mn −I are exposed to nucleophiles and electrophiles, respectively, while Mn0 facilitates the radical cycloisomerization catalysis of 6-iodo-1- hexene at room temperature. Furthermore, this work underscores the importance of ligand sterics in rationalizing reactivity patterns at Mn and provides valuable insights for designing chelating ligands that can selectively leverage Mn I/0/‑I states in redox-mediated catalytic reactions.
We observed the X-ray nova A0620-00 with the Hubble Space Telescope (HST) Faint object Spectrograph 16 yr after its 1975 outburst. We present a single spectrum (1250-4750 A), which is approximately an average over a full 7.8 hr orbital cycle of the source. The continuum can be fitted approximately by a blackbody model with T = 9000 K and a small projected source area, which is approximately 1 % of the expected area of the accretion disk. AS0620-00 is faint in the far-UV band; its luminosity is comparable to the luminosity of the quiescent dwarf-nova accretion disk (i.e., excluding the white dwarf). By analogy with dwarf novae, the optical luminosity of the disk (M(sub nu) approximately = 7) and the orbital period of A0620-00 imply that the rate of mass transfer onto the outer disk in M(sub d) approximately 10(exp -10) solar mass/yr. We also observed A0620-00 with the ROSAT PSPC X-ray detector for 3 x 10(exp 4) s and detected a faint source (5 sigma) at the location of the X-ray nova. For an assumed blackbody spectrum the source temperature and luminosity are approximately 0.16 keV and 6 x 10(exp 30) ergs/s, respectively (d = 1 kpc). This luminosity implies that the rate of mass transfer into the black hole is extraordinarily small: M(sub BH) less than 5 x 10(exp -15) solar mass/yr. The much larger mass transfer rate onto the outer disk, and the UV/X-ray faintness of the inner disk confirm key predictions of the disk instability model for the nova outburst of A0620-00 published by Huang and Wheeler and by Mineshige and Wheeler.
On 2019 August 14, the Advanced LIGO and Virgo interferometers detected the high-significance gravitational wave (GW) signal S190814bv. The GW data indicated that the event resulted from a neutron star–black hole (NSBH) merger, or potentially a low-mass binary BH merger. Due to the low false-alarm rate and the precise localization (23 deg^(2) at 90%), S190814bv presented the community with the best opportunity yet to directly observe an optical/near-infrared counterpart to an NSBH merger. To search for potential counterparts, the GROWTH Collaboration performed real-time image subtraction on six nights of public Dark Energy Camera images acquired in the 3 weeks following the merger, covering >98% of the localization probability. Using a worldwide network of follow-up facilities, we systematically undertook spectroscopy and imaging of optical counterpart candidates. Combining these data with a photometric redshift catalog, we ruled out each candidate as the counterpart to S190814bv and placed deep, uniform limits on the optical emission associated with S190814bv. For the nearest consistent GW distance, radiative transfer simulations of NSBH mergers constrain the ejecta mass of S190814bv to be M(ej) < 0.04 Mꙩ at polar viewing angles, or M(ej) < 0.03 Mꙩ if the opacity is κ < 2 sq.cm/g. Assuming a tidal deformability for the NS at the high end of the range compatible with GW170817 results, our limits would constrain the BH spin component aligned with the orbital momentum to be χ < 0.7 for mass ratios Q < 6, with weaker constraints for more compact NSs.
Using early data from the Dark Energy Spectroscopic Instrument (DESI) survey, we search for active galactic nuclei (AGN) signatures in 410,757 line-emitting galaxies. By employing the BPT emission-line ratio diagnostic diagram, we identify AGNs in 75,928/296,261 (≈25.6%) high-mass ($\mathrm{log}({M}_{\star }/{M}_{\odot })\,\gt$ 9.5) and 2444/114,496 (≈2.1%) dwarf ($\mathrm{log}({M}_{\star }/{M}_{\odot })\,\leqslant$ 9.5) galaxies. Of these AGN candidates, 4181 sources exhibit a broad Hα component, allowing us to estimate their BH masses via virial techniques. This study more than triples the census of dwarf AGNs and doubles the number of intermediate-mass black hole (M BH ≤ 10 6 M ⊙ ) candidates, spanning a broad discovery space in stellar mass (7 $\lt \mathrm{log}({M}_{\star }/{M}_{\odot })\,\lt$ 12) and redshift (0.001 < z < 0.45). The observed AGN fraction in dwarf galaxies (≈2.1%) is nearly four times higher than prior estimates, primarily due to DESI’s smaller fiber size, which enables the detection of lower-luminosity dwarf AGN candidates. We also extend the M BH –M⋆ scaling relation down to ${\rm{log}}({M}_{\star }/{M}_{\odot })\,\approx$ 8.5 and $\mathrm{log}({M}_{\mathrm{BH}}/{M}_{\odot })\,\approx$ 4.4, with our results aligning well with previous low-redshift studies. The large statistical sample of dwarf AGN candidates from current and future DESI releases will be invaluable for enhancing our understanding of galaxy evolution at the low-mass end of the galaxy mass function.
Recent studies have revealed strong correlations between 1-10 Hz frequencies of quasiperiodic oscillations (QPOs) and the spectral power law index of several Black Hole (BH) candidate sources when seen in the low/hard state, the steep power-law (soft) state, and in transition between these states. In the soft state these index-QPO frequency correlations show a saturation of the photon index GAMMA approximately equal to 2.7 at high values of the low frequency nu(sub L). This saturation effect was previously identified as a black hole signature. In this paper we argue that this saturation does not occur, at least for one neutron star (NS) source 4U 1728-34, for which the index GAMMA monotonically increases with nu(sub L) to the values of 6 and higher. We base this conclusion on our analysis of approximately 1.5 Msec of RXTE archival data for 4U 1728-34. We reveal the spectral evolution of the Comptonized blackbody spectra when the source transitions from the hard to soft states. The hard state spectrum is a typical thermal Comptonization spectrum of the soft photons which originate in the disk and the NS outer photospheric layers. The hard state photon index is GAMMA approximately 2. The soft state spectrum consists of two blackbody components which are only slightly Comptonized. Thus we can claim (as expected from theory) that in NS sources thermal equilibrium is established for the soft state. To the contrary in BH sources, the equilibrium is never established due to the presence of the BH horizon. The emergent BH spectrum, even in the high/soft state, has a power law component. We also identify the low QPO frequency nu(sub L) as a fundamental frequency of the quasi-spherical component of the transition layer (presumably related to the corona and the NS and disk magnetic closed field lines). The lower frequency nu(sub SL) is identified as the frequency of oscillations of a quasi-cylindrical configuration of the TL (presumably related to the NS and disk magnetic open field lines). We also show that the presence of Fe K(sub alpha), emission-line strengths, QPOs, and the link between them does not depend on radio flux in 4U 1728-34.
We present results from an approximately equal 100 ks Chandra observation of the 2QZ Cluster 1004+00 structure at z = 2.23 (hereafter 2QZ Clus). 2QZ Clus was originally identified as an overdensity of four optically-selected QSOs at z = 2.23 within a 15 × 15 arcmin square region. Narrow-band imaging in the near-IR (within the K band) revealed that the structure contains an additional overdensity of 22 z = 2.23 H alpha-emitting galaxies (HAEs), resulting in 23 unique z = 2.23 HAEs/QSOs (22 within the Chandra field of view). Our Chandra observations reveal that three HAEs in addition to the four QSOs harbor powerfully accreting supermassive black holes (SMBHs), with 2-10 keV luminosities of approximately equal (8-60) × 10(exp 43) erg s(exp−1) and X-ray spectral slopes consistent with unobscured active galactic nucleus (AGN). Using a large comparison sample of 210 z = 2.23 HAEs in the Chandra-COSMOS field (C-COSMOS), we find suggestive evidence that the AGN fraction increases with local HAE galaxy density. The 2QZ Clus HAEs reside in a moderately overdense environment (a factor of approximately equal 2 times over the field), and after excluding optically-selected QSOs, we find that the AGN fraction is a factor of approximately equal 3.5(+3.8/ −2.2) times higher than C-COSMOS HAEs in similar environments. Using stacking analyses of the Chandra data and Herschel SPIRE observations at 250micrometers, we respectively estimate mean SMBH accretion rates ( M(BH)) and star formation rates (SFRs) for the 2QZ Clus and C-COSMOS samples. We find that the mean 2QZ Clus HAE stacked X-ray luminosity is QSO-like (L(2−10 keV) approximately equal [6-10] × 10(exp 43) erg s(exp −1)), and the implied M(BH)/SFR approximately equal (1.6-3.2) × 10(exp −3) is broadly consistent with the local M(BH)/Stellar Mass relation and z approximately equal 2 X-ray selected AGN. In contrast, the C-COSMOS HAEs are on average an order of magnitude less X-ray luminous and have M(BH)/SFR approximately equal (0.2-0.4) × 10(exp −3), somewhat lower than the local MBH/M relation, but comparable to that found for z approximately equal 1-2 star-forming galaxies with similar mean X-ray luminosities. We estimate that a periodic QSO phase with duty cycle approximately 2%-8% would be sufficient to bring star-forming galaxies onto the local M(BH)/Stellar Mass relation. This duty cycle is broadly consistent with the observed C-COSMOS HAE AGN fraction (Approximately equal 0.4%-2.3%) for powerful AGN with LX approximately greater than 10(exp 44) erg s(exp −1). Future observations of 2QZ Clus will be needed to identify key factors responsible for driving the mutual growth of the SMBHs and galaxies.
Abstract In the last decade, there have been several discoveries of active galactic nuclei (AGN) in dwarf galaxies including an AGN in an ultracompact dwarf galaxy with a black hole mass >10 6 M ⊙ . However, finding a supermassive black hole (SMBH) in a dwarf low surface brightness (LSB) galaxy is rare. We report the discovery of a Seyfert type 2 class AGN that is associated with a nuclear SMBH of mass ∼6.5 × 10 6 M ⊙ in a dwarf LSB galaxy (μ 0,r > 23.8 mag arcsec −2 ) that we denote by MJ0818+2257. The galaxy was previously thought to be an outlying emission blob around the large spiral galaxy LEDA 1678924. In our current analysis, which includes the detection of the optical counterpart of MJ0818+2257, we study its ionized gas kinematics and find that the dynamical mass within the ionized gas disk is ∼5.3 × 10 9 M ⊙ . This is comparable to its stellar mass, which is ∼3 × 10 9 M ⊙ , and suggests that MJ0818+2257 is moderately dark matter dominated within the stellar disk. The SMBH-mass-to-galaxy-stellar-mass ratio isM BH /M(*) > 0.022, which is high compared to disk galaxies. Our detection of an SMBH in a bulgeless LSB dwarf galaxy raises questions about the growth of SMBHs in low-luminosity galaxies and suggests the possibility of detecting heavy seed black holes from early epochs in LSB dwarf galaxies in the low-redshift Universe.
We present late time multi-wavelength observations of Swift J1644+57, suggested to be a relativistic tidal disruption flare (TDF). Our observations extend to greater than 4 years from discovery and show that 1.4 years after outburst the relativistic jet switched off on a timescale less than tens of days, corresponding to a power-law decay faster than t (sup -70). Beyond this point weak X-rays continue to be detected at an approximately constant luminosity of L (sub X) approximately equal to 5 times 10 (sup 42) ergs per second and are marginally inconsistent with a continuing decay of t (sup minus 5 divided by 3), similar to that seen prior to the switch-off. Host photometry enables us to infer a black hole mass of M (mass) (sub BH (black hole) equal to 3 times 10 (sup 6) the mass of the sun, consistent with the late time X-ray luminosity arising from sub-Eddington accretion onto the black hole in the form of either an unusually optically faint active galactic nucleus or a slowly varying phase of the transient. Optical/IR observations show a clear bump in the light curve at timescales of 30 to 50 days, with a peak magnitude (corrected for host galaxy extinction) of M (sub R) approximately equal to minus 22 to minus 23. The luminosity of the bump is significantly higher than seen in other, nonrelativisticTDFs and does not match any re-brightening seen at X-ray or radio wavelengths. Its luminosity, light curve shape, and spectrum are broadly similar to those seen in superluminous supervnovae, although subject to large uncertainties in the correction of the significant host extinction. We discuss these observations in the context of both TDF and massive star origins for Swift J1644+5734 and other candidate relativistic tidal flares.
On 2019 August 14, the Advanced LIGO and Virgo interferometers detected the high-significance gravitational wave (GW) signal S190814bv. The GW data indicated that the event resulted from a neutron star–black hole (NSBH) merger, or potentially a low-mass binary BH merger. Due to the low false-alarm rate and the precise localization (23 deg 2 at 90%), S190814bv presented the community with the best opportunity yet to directly observe an optical/near-infrared counterpart to an NSBH merger. To search for potential counterparts, the GROWTH Collaboration performed real-time image subtraction on six nights of public Dark Energy Camera images acquired in the 3 weeks following the merger, covering >98% of the localization probability. Using a worldwide network of follow-up facilities, we systematically undertook spectroscopy and imaging of optical counterpart candidates. Combining these data with a photometric redshift catalog, we ruled out each candidate as the counterpart to S190814bv and placed deep, uniform limits on the optical emission associated with S190814bv. For the nearest consistent GW distance, radiative transfer simulations of NSBH mergers constrain the ejecta mass of S190814bv to be M ej < 0.04 M ⊙ at polar viewing angles, or M ej < 0.03 M ⊙ if the opacity is κ < 2 cm 2 g -1 . Assuming a tidal deformability for the NS at the high end of the range compatible with GW170817 results, our limits would constrain the BH spin component aligned with the orbital momentum to be χ < 0.7 for mass ratios Q < 6, with weaker constraints for more compact NSs.