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At least 1,351 records · Page 75

Evidence for X-Ray Emission in Excess to the Jet-afterglow Decay 3.5 yr after the Binary Neutron Star Merger GW 170817: A New Emission Component

For the first ~3 yrs after the binary neutron star merger event GW 170817, the radio and X-ray radiation has been dominated by emission from a structured relativistic off-axis jet propagating into a low-density medium with n < 0.01 cm -3 . We report on observational evidence for an excess of X-ray emission at δt > 900 days after the merger. With L x ≈ 5 × 10 38 erg s -1 at 1234 days, the recently detected X-ray emission represents a ≥ 3.2σ (Gaussian equivalent) deviation from the universal post-jet-break model that best fits the multiwavelength afterglow at earlier times. In the context of JetFit afterglow models, current data represent a departure with statistical significance ≥ 3.1σ, depending on the fireball collimation, with the most realistic models showing excesses at the level of ≥ 3.7σ. A lack of detectable 3 GHz radio emission suggests a harder broadband spectrum than the jet afterglow. These properties are consistent with the emergence of a new emission component such as synchrotron radiation from a mildly relativistic shock generated by the expanding merger ejecta, i.e., a kilonova afterglow. In this context, we present a set of ab initio numerical relativity binary neutron star (BNS) merger simulations that show that an X-ray excess supports the presence of a high-velocity tail in the merger ejecta, and argues against the prompt collapse of the merger remnant into a black hole. Radiation from accretion processes on the compact-object remnant represents a viable alternative. Neither a kilonova afterglow nor accretion-powered emission have been observed before, as detections of BNS mergers at this phase of evolution are unprecedented

79 ASTRONOMY AND ASTROPHYSICS↗

Discovery of Nearly Coherent Oscillations with a Frequency of approximately 567 Hz During Type I X-ray Bursts of the X-ray Transient and Eclipsing Binary X1658-298

We report the discovery of nearly coherent oscillations with a frequency of approximately 567 Hz during type I X-ray bursts from the X-ray transient and eclipsing binary X1658-298. If these oscillations are directly related to the neutron star rotation, then the spin period of the neutron star in X1658-298 is approximately 1.8 ms. The oscillations can be present during the rise or decay phase of the bursts. Oscillations during the decay phase of the bursts show an increase in frequency of approximately 0.5-1 Hz. However, in one particular burst the oscillations reappear at the end of the decay phase at about 571.5 Hz. This represents an increase in oscillation frequency of about 5 Hz, which is the largest frequency change seen so far in a burst oscillation. It is unclear if such a large change can be accommodated by present models used to explain the frequency evolution of the oscillations. The oscillations at 571.5 Hz are unusually soft compared to the oscillations found at 567 Hz. We also observed several bursts during which the oscillations are detected at much lower significance or not at all. Most of these bursts happen during periods of X-ray dipping behavior, suggesting that the X-ray dipping might decrease the amplitude of the oscillations (although several complications exist with this simple picture). We discuss our discovery in the framework of the neutron star spin interpretation.

Wijnands, Rudy↗

The Effectiveness of TAG or Guard-Gates in SET Suppression Using Delay and Dual-Rail Configurations at 0.35 microns

Design options for decreasing the susceptibility of integrated circuits to Single Event Upset (SEU) fall into two categories: (1) increasing the critical charge to cause an upset at a particular node, and (2) employing redundancy to mask or correct errors. With decreasing device sizes on an Integrated Circuit (IC), the amount of charge required to represent a logic state has steadily reduced. Critical charge methods such as increasing drive strength or increasing the time required to change state as in capacitive or resistive hardening or delay based approaches extract a steadily increasing penalty as a percentage of device resources and performance. Dual redundancy is commonly assumed only to provide error detection with Triple Modular Redundancy (TMR) required for correction, but less well known methods employ dual redundancy to achieve full error correction by voting two inputs with a prior state to resolve ambiguity. This requires special circuits such as the Whitaker latch [1], or the guard-gate [2] which some of us have called a Transition AND Gate (TAG) [3]. A 2-input guard gate is shown in Figure 1. It is similar to a Muller Completion Element [4] and relies on capacitance at node "out" to retain the prior state when inputs disagree, while eliminating any output buffer which would be susceptible to radiation strikes. This paper experimentally compares delay based and dual rail flip-flop designs wherein both types of circuits employ guard-gates to optimize layout and performance, and draws conclusions about design criteria and suitability of each option. In both cases a design goal is protection against Single Event Transients (SET) in combinational logic as well as SEU in the storage elements. For the delay based design, it is also a goal to allow asynchronous clear or preset inputs on the storage elements, which are often not available in radiation tolerant designs.

Shuler, Robert L.↗

Discovery of the 198 s X-Ray Pulsar GRO J2058+42

GRO J2058+42, a transient 198 second x-ray pulsar, was discovered by the Burst and Transient Source Experiment (BATSE) on the Compton Gamma-Ray Observatory (CGRO), during a "giant" outburst in 1995 September-October. The total flux peaked at about 300 mCrab (20-50 keV) as measured by Earth occultation. The pulse period decreased from 198 s to 196 s during the 46-day outburst. The pulse shape evolved over the course of the outburst and exhibited energy dependent variations. BATSE observed five additional weak outbursts from GRO J2058+427 each with two week duration and peak pulsed flux of about 15 mcrab (20-50 keV), that were spaced by about 110 days. An observation of the 1996 November outburst by the Rossi X-ray Timing Explorer (RXTE) Proportional Counter Array (PCA) localized the source to within a 4' radius error circle (90% confidence) centered on R.A. = 20 h 59 m.0, Decl. = 41 deg 43 min (J2000). Additional shorter outbursts with peak pulsed fluxes of about 8 mCrab were detected by BATSE halfway between the first four 15 mCrab outbursts. The RXTE All-Sky Monitor detected 8 weak outbursts with approximately equal durations and intensities. GRO J2058+42 is most likely a Be/X-ray binary that appears to outburst at periastron and apastron. No optical counterpart has been identified to date and no x-ray source was present in the error circle in archival ROSAT observations.

Wilson, Colleen A.↗

Discovery of the 198 Second X-Ray Pulsar GRO J2058+42

GRO J2058+42, a transient 198 s X-ray pulsar, was discovered by the Burst and Transient Source Experiment (BATSE) on the Compton Gamma Ray Observatory (CGRO) during a "giant" outburst in 1995 September-October. The total flux peaked at about 300 mcrab (20-50 keV) as measured by Earth occultation. The pulse period decreased from 198 to 196 s during the 46 day outburst. The pulse shape evolved over the course of the outburst and exhibited energy-dependent variations. BATSE observed five additional weak outbursts from GRO J2058 + 42, each with a 2 week duration and a peak-pulsed flux of about 15 mcrab (20-50 keV), that were spaced by about 110 days. An observation of the 1996 November outburst by the Rossi X-Ray Timing Explorer (RXTE) proportional counter array (PCA) localized the source to within a 4 s radius error circle (90% confidence) centered on R.A. = 20h 59m.0, decl. = 41 deg 43 s (J2000). Additional shorter outbursts with peak-pulsed fluxes of about 8 mcrab were detected by BATSE halfway between the first four 15 mcrab outbursts. The RXTE All-Sky Monitor detected all eight weak outbursts with approximately equal durations and intensities. GRO J2058 + 42 is most likely a Be/X-ray binary that appears to outburst at periastron and apastron, No optical counterpart has been identified to date, and no X-ray source was present in the error circle in archival ROSAT observations.

Wilson, Colleen A.↗

A giant umbrella-like stellar stream around the tidal ring galaxy NGC 922

Tidal ring galaxies (TRGs) are rarely observed in the local universe due to their intrinsically transient nature. The tidal ring structures are the result of strong interactions between gas-rich stellar disks and smaller galactic systems, and do not last longer than ~500 Myr. Therefore, these are perfect scenarios in which to look for the debris of recently accreted dwarf galactic systems. Our goal is to study the low surface brightness stellar structures around the TRG NGC 922 and to revise the hypothesis of its formation in light of these new data. We present new deep images of the TRG NGC 922 and its surroundings from the DESI Legacy survey data and from our observations with an amateur telescope. These observations are compared with results from high-resolution N-body simulations that were designed to reproduce an alternative formation scenario for this peculiar galaxy. Our new observations unveil that the low surface brightness stellar tidal structures around NGC 922 are much more complex than reported in previous works. In particular, the formerly detected tidal spike-like structure at the north-east of the central galaxy disk is not connected with the dwarf companion galaxy PGC 3080368, which has been suggested as the intruder triggering the ring formation of NGC 922. The deep images reveal that this tidal structure mainly has a fainter giant umbrella-like shape, and thus it was formed from the tidal disruption of a different satellite. Using the broad-band g, r, and z DESI LS images, we measured the photometric properties of this stellar stream, estimating a total absolute magnitude in the r band of M r = -17.0 ± 0.03 mag and a total stellar mass for the stream of between 6.9 and 8.5×10 8 M ⊙ . We performed a set of N-body simulations to reproduce the observed NGC922-intruder interaction, suggesting a new scenario for the formation of its tidal ring from the infall of a gas-rich satellite around 150 Myr ago. Finally, our deep images also reveal a tidal shell around the dwarf galaxy PGC 3080368, a possible fossil of a recent merger with a smaller satellite, which may suggest it is in its first infall towards NGC 922.

79 ASTRONOMY AND ASTROPHYSICS↗

SATS Transient Fission Gas Release Test with Irradiated Fuel under Loss of Coolant Accident Conditions

The transient fission gas release (tFGR) during the temperature ramp associated with a loss-of-coolant accident (LOCA) in light-water reactors (LWRs) is likely a significant contribution to the total pressure in a fuel rod and may cause an unexpected rod burst. The lack of data related to tFGR continues to be a key gap in understanding LWR cladding burst behavior under LOCA conditions. To fully characterize this behavior, tFGR data must be collected from several different systems that can capture all relevant testing conditions. Oak Ridge National Laboratory (ORNL) has developed a system to measure the integral tFGR from irradiated fuel segments. This system was designed to integrate with the existing Severe Accident Test Station (SATS) and to build upon decades of experience capturing fission gas to characterize fuel behavior. The tFGR system consists of a sweep gas system to transport gases from the in-cell SATS apparatus to an out-of-cell fission gas detection system composed of a series of cold traps to capture the off-gas from the heating tests and a gamma spectrometry system to detect and measure 85 Kr. Initial system testing operations were completed during which 85 Kr collection and measurement were verified along with the ability to detect stable inert gases. A tFGR test with a high-burnup fuel specimen was successfully conducted by the in-cell SATS-tFGR system at ORNL. The posttest examination is under way, the result of which will be reported in FY24.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Can we identify lensed gamma-ray bursts?

A gravitationally lensed gamma-ray burst (GRB) would appear as multiple bursts with identical light curves, separated in time and differing only by the scaling of their amplitudes. In reality, the detected bursts will be noisy, and therefore they may be difficult to identify as lensed images. Furthermore, faint, intrinsically similar, yet distinct light curves may be falsely identified as lensing events. In this paper we develop two statistical tests to distinguish noisy burst light curves. We use Fourier analysis techniques to analyze the signals for both intrinsic variability and variability due to noise. We are able to determine the noise level, and we compare the bursts only at frequency channels that are signal dominated. Utilizing these methods, we are able to make quantitative statements about whether two bursts are distinct. We apply these statistics to scaled versions of two subbursts of GRB 910503 -- subbursts previously investigated by Wambsganss using a different statistical test. We find that our methods are able to distinguish these bursts at slightly smaller amplitudes than those at which Wambsganss's method succeeds. We then apply our techniques to 'candidate' lensing events taken from the Burst and Transient Source Experiment (BATSE) catalog, and we find that nearly all of them, except for the very shortest ones (durations approx. less than 3 sec), are distinguishable. We therefore expect that a majority of bursts will be distinguishable from one another.

Nowak, Michael A.↗

Anharmonic Exciton‐Phonon Coupling in Metal‐Organic Chalcogenides Hybrid Quantum Wells

Abstract In contrast to inorganic quantum wells, hybrid quantum wells (HQWs) based on metal‐organic semiconductors are characterized by relatively soft lattices, in which excitonic states can strongly couple to lattice phonons. Therefore, understanding the lattice's impact on exciton dynamics is essential for harnessing the optoelectronic potential of HQWs. Beyond 2D metal halide perovskites, layered metal‐organic chalcogenides (MOCs), which are an air‐stable, underexplored material class hosting room‐temperature excitons, can be exploited as photodetectors, light emitting devices, and ultrafast photoswitches. Here, the role of phonons in the optical transitions of the prototypical MOC [AgSePh] ∞ is elucidated. Impulsive stimulated Raman scattering (ISRS) allows the detection of coherent exciton oscillations driven by Fröhlich interaction with low‐energy optical phonons. Steady state absorption and Raman spectroscopies reveal a strong exciton‐phonon coupling (Huang‐Rhys parameter ≈1.7) and its anharmonicity, manifested as a nontrivial temperature‐dependent Stokes shift. The ab initio calculations support these observations, hinting at an anharmonic behavior of the low‐energy phonons <200 cm −1 . These results untangle complex exciton‐phonon interactions in MOCs, establishing an ideal testbed for room‐temperature many‐body phenomena.

36 MATERIALS SCIENCE↗

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti–O●−) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance—a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode’s cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3 ps and a time constant of 0.48 ± 0.09 ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Chemistry↗

Effects of orbital spaceflight on human osteoblastic cell physiology and gene expression

During long-term spaceflight, astronauts lose bone, in part due to a reduction in bone formation. It is not clear, however, whether the force imparted by gravity has direct effects on bone cells. To examine the response of bone forming cells to weightlessness, human fetal osteoblastic (hFOB) cells were cultured during the 17 day STS-80 space shuttle mission. Fractions of conditioned media were collected during flight and shortly after landing for analyses of glucose utilization and accumulation of type I collagen and prostaglandin E(2) (PGE(2)). Total cellular RNA was isolated from flight and ground control cultures after landing. Measurement of glucose levels in conditioned media indicated that glucose utilization occurred at a similar rate in flight and ground control cultures. Furthermore, the levels of type I collagen and PGE(2) accumulation in the flight and control conditioned media were indistinguishable. The steady-state levels of osteonectin, alkaline phosphatase, and osteocalcin messenger RNA (mRNA) were not significantly changed following spaceflight. Gene-specific reductions in mRNA levels for cytokines and skeletal growth factors were detected in the flight cultures using RNase protection assays. Steady-state mRNA levels for interleukin (IL)-1alpha and IL-6 were decreased 8 h following the flight and returned to control levels at 24 h postflight. Also, transforming growth factor (TGF)-beta(2) and TGF-beta(1) message levels were modestly reduced at 8 h and 24 h postflight, although the change was not statistically significant at 8 h. These data suggest that spaceflight did not significantly affect hFOB cell proliferation, expression of type I collagen, or PGE(2) production, further suggesting that the removal of osteoblastic cells from the context of the bone tissue results in a reduced ability to respond to weightlessness. However, spaceflight followed by return to earth significantly impacted the expression of cytokines and skeletal growth factors, which have been implicated as mediators of the bone remodeling cycle. It is not yet clear whether these latter changes were due to weightlessness or to the transient increase in loading resulting from reentry.

Non-NASA Center↗

XTE J1906+09 Observations with RXTE

The 89 s pulsar XTE J1906+09 was serendipitously discovered in a 1996 observation of the soft gamma repeater SGR 1900+14. Two outbursts, in 1996 September and 1998 September have been reported to date. Since this system appears to be transient, it is likely in a Be/X-ray binary, accreting material from a circumstellar disk around its companion. Preliminary pulse timing analyses of RXTE data from the 1998 September outburst revealed an orbital signature consistent with either (i) a low-eccentricity, short period orbit, similar to OAO 1657-415 or (ii) periastron passage in a longer orbital period, higher eccentricity Be/X-ray binary system. No companion has been identified to date due to the large 2 feet error radius of the current best position. SGR 1900+14 has been regularly monitored with RXTE since 1998. Because XTE J1906+09 is only 33 feet away, it often shares the RXTE/PCA field of view with SGR 1900+14, giving us a large number of archival PCA observations. We will present results of a search of RXTE data for outbursts of XTE 1906+09, including histories of pulse frequency, 2-30 keV intensity, pulse profiles, and energy spectra. Results of a pulse timing analysis of the detected outbursts will also be presented.

Wilson, Colleen A.↗

An Extreme X-ray Disk Wind in the Black Hole Candidate IGR J17091-3624

Chandra spectroscopy of transient stellar-mass black holes in outburst has clearly revealed accretion disk winds in soft, disk-dominated states, in apparent anti-correlation with relativistic jets in low/hard states. These disk winds are observed to be highly ionized. dense. and to have typical velocities of approx 1000 km/s or less projected along our line of sight. Here. we present an analysis of two Chandra High Energy Transmission Grating spectra of the Galactic black hole candidate IGR J17091-3624 and contemporaneous EVLA radio observations. obtained in 2011. The second Chandra observation reveals an absorption line at 6.91+/-0.01 keV; associating this line with He-like Fe XXV requires a blue-shift of 9300(+500/-400) km/ s (0.03c. or the escape velocity at 1000 R(sub schw)). This projected outflow velocity is an order of magnitude higher than has previously been observed in stellar-mass black holes, and is broadly consistent with some of the fastest winds detected in active galactic nuclei. A potential feature at 7.32 keV, if due to Fe XXVI, would imply a velocity of approx 14600 km/s (0.05c), but this putative feature is marginal. Photoionization modeling suggests that the accretion disk wind in IGR J17091-3624 may originate within 43,300 Schwarzschild radii of the black hole, and may be expelling more gas than accretes. The contemporaneous EVLA observations strongly indicate that jet activity was indeed quenched at the time of our Chandra observations. We discuss the results in the context of disk winds, jets, and basic accretion disk physics in accreting black hole systems

King, A. L.↗

Improved Modelling of SEP Event Onset Within the WSA–Enlil–SEPMOD Framework

Multi-spacecraft observations of solar energetic particle (SEP) events not only enable a deeper understanding and development of particle acceleration and transport theories but also provide important constraints for model validation efforts. However, because of computational limitations, a given physics-based SEP model is usually best suited to capture a particular phase of an SEP event, rather than its whole development from onset through decay. For example, magnetohydrodynamic (MHD) models of the heliosphere often incorporate solar transients only at the outer boundary of their so-called coronal domain – usually set at a heliocentric distance of 20–30 R⊙. This means that particle acceleration at coronal mass ejection (CME)-driven shocks is also computed from this boundary onwards, leading to simulated SEP event onsets that can be many hours later than observed, since shock waves can form much lower in the solar corona. In this work, we aim to improve the modelled onset of SEP events by inserting a “fixed source” of particle injection at the outer boundary of the coronal domain of the coupled WSA–Enlil 3D MHD model of the heliosphere. The SEP model that we employ for this effort is Solar Energetic Particle MODel (SEPMOD), a physics-based test-particle code based on a field line tracer and adiabatic invariant conservation. We apply our initial tests and results of SEPMOD’s fixed-source option to the 2021 October 9 SEP event, which was detected at five well-separated locations in the inner heliosphere – Parker Solar Probe, STEREO-A, Solar Orbiter, BepiColombo, and near-Earth spacecraft.

Solar eruptions↗

Transient Studies of CO 2 Adsorption over CeO 2 Nanostructures with In Situ DRIFTS and Modulation Excitation

Experiments of in-situ DRIFTS combined with modulation excitation (ME) spectroscopy showed a rich surface chemistry associated with the adsorption of CO 2 on nanocubes and nanospheres of ceria. The nanocubes exposed faces with a (100) orientation, with the edges and corners displaying (110) and (111) orientations, respectively. Here, the nanospheres mainly contained ceria (111) and (110) planes. DFT calculations showed that CO 2 is a multidentate adsorbate on ceria that can undergo changes in its bonding configuration depending on the chemical environment. At 250 °C, a temperature typically used for the conversion of CO 2 into oxygenates, alkanes and olefins, CO 2 reacted with O centers or OH groups present on the nanocubes and nanospheres to yield bi- and tri-dentate carbonates, hydroxycarbonates, and formates. Both nanostructures were highly reactive and a dynamic equilibrium was established: carbonate species were rapidly generated upon the injection of CO 2 and they decomposed upon the removal of CO 2 from the gas phase. In the case of the ceria nanocubes, the adsorption/desorption processes were essentially reversible, opening the door to catalytic transformations. A larger concentration of defects in the ceria nanospheres led to strongly bound carbonates and formates that may be spectators, site blockers, or surface modifiers in catalytic processes. In the ME studies, additional intermediates were detected, and it was clear that the response of surface species to the presence/absence of CO 2 was highly dependent on the morphology of the ceria nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gamma-ray signatures of 𝑟-process radioactivity from the collapse of magnetized white dwarfs

We predict the gamma-ray line emission from 𝑟-process nuclei synthesized in the ejecta of the accretion-induced collapse (AIC) of a magnetized, rapidly rotating white dwarf. Using ejecta from a two-dimensional general-relativistic neutrino-magnetohydrodynamic simulation, further evolved with a radiation-hydrodynamics code coupled to an in situ nuclear reaction network, we construct angle-dependent gamma-ray spectra in the 0.01–10 MeV band via composition-dependent ray tracing through the ejecta. The emission between ∼1 and 10 d is dominated by 132 I (𝑡 1/2 = 2.3 h), continuously replenished by the decay of its parent 132 Te (𝑡 1/2 = 3.2 d), with additional contributions from 131 I, 133 Xe, and 132 Te . At 𝑡 ≳ 20 d, 56 Co (from 56 Ni decay) becomes the primary emitter. The simultaneous presence of 𝑟 process and iron-peak gamma-ray lines is distinctive of AIC ejecta and absent in binary neutron star mergers, where iron-peak nuclei are generally not synthesized. Comparing with the 3⁢𝜎 continuum sensitivities of planned MeV gamma-ray telescopes (COSI, AMEGO-X, e-ASTROGAM, GRAMS, GammaTPC), we find the brightest 𝑟-process lines detectable to ∼10 Mpc by GammaTPC and GRAMS, with the signal approaching their sensitivity threshold at 30 Mpc. As a result, the 𝑟-process spectral features survive time integration over ∼30 d exposures, demonstrating robustness against the long observation times required by gamma-ray detectors.

Nuclear reactions↗

The Ancient Martian Climate System

Today Mars is a cold, dry, desert planet. The atmosphere is thin and liquid water is not stable at the surface. But there is evidence that very early in its history, some 3.7-4.1 billion years ago, the climate system supported much warmer conditions including an active hydrological cycle with rainfall and runoff. Given the importance of liquid water to astrobiology and NASA’s Mars Exploration Program, researchers have been trying to understand the ancient martian climate system since the early 1970s when the Mariner 9 spacecraft first detected fluvial features on its oldest terrains. Though the evidence for warm wet conditions is compelling, the problem is not yet solved. The main issue is coping with the faint young sun. During the period when warmer conditions prevailed the sun’s luminosity was ~25% less than it is today. How can we explain the presence of liquid water on the surface of ancient Mars under such conditions? A similar problem exists for Earth, which would have frozen over under a faint sun even though the evidence suggests otherwise. Attempts to solve the “Faint Young Sun Paradox”, as it is commonly known, rely on greenhouse warming from an atmosphere with a different mass and composition than we see today. This is true for both Mars and Earth. However, for Mars there is no solution in sight. Long-lived continuously warm and wet atmospheres are difficult to produce and sustain. And a new and emerging idea - that ancient Mars was fundamentally a cold planet with transient episodes of warm wet conditions brought about by external forcings such as impacts, volcanism, and/or orbital changes – also has issues. In this seminar I will review this fascinating topic and discuss some of the recent ideas on how to solve it, the issues they raise, and what I believe are some promising avenues for future research.

Haberle, Robert M.↗

Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO 2 to Formate by Ruthenium Complexes

We show a series of 4,4'-dimethyl-2,2'-bipyridyl ruthenium complexes with carbonyl ligands were prepared and studied using a combination of electrochemical and spectroscopic methods with infrared detection to provide structural information on reaction intermediates in the photochemical reduction of CO 2 to formate in acetonitrile (CH 3 CN). An unsaturated 5-coordinate intermediate was characterized, and the hydride-transfer step to CO 2 from a singly reduced metal-hydride complex was observed with kinetic resolution. While triethanolamine (TEOA) was expected to act as a proton acceptor to ensure the sacrificial behavior of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as an electron donor, time-resolved infrared measurements revealed that about 90% of the photogenerated one-electron reduced complexes undergo unproductive back electron transfer. Furthermore, TEOA showed the ability to capture CO 2 from CH 3 CN solutions to form a zwitterionic alkylcarbonate adduct and was actively engaged in key catalytic steps such as metal-hydride formation, hydride transfer to CO 2 to form the bound formate intermediate, and dissociation of formate ion product. Collectively, the data provide an overview of the transient intermediates of Ru(II) carbonyl complexes and emphasize the importance of considering the participation of TEOA when investigating and proposing catalytic pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗