Resonant Auger decay of iodobenzene below the I 4d edge.

New data are presented on the resonant Auger decay of iodobenzene (C6H5I) in the region of the I 4d-1 ionization threshold. The excited molecules decay by participator and spectator processes to populate single-hole valence states and two-hole, one-particle excited states of the cation, providing new information on the structure of C6H5I+. Excitation of dissociative C6H5I (I 4d5/2,3/2-1)σ* resonances can, in principle, result in ultrafast dissociation to C6H5 + I** and the subsequent autoionization of I**, but no evidence for this process is observed. The results are compared with our recent study of the resonant Auger decay of methyl iodide (CH3I).

Deconvolution of the X-ray absorption spectrum of trans-1,3-butadiene with resonant Auger spectroscopy.

High-resolution carbon K-edge X-ray photoelectron, X-ray absorption, non-resonant and resonant Auger spectra are presented of gas phase trans-1,3-butadiene alongside a detailed theoretical analysis utilising nuclear ensemble approaches and vibronic models to simulate the spectroscopic observables. The resonant Auger spectra recorded across the first pre-edge band reveal a complex evolution of different electronic states which remain relatively well-localised on the edge or central carbon sites. The results demonstrate the sensitivity of the resonant Auger observables to the weighted contributions from multiple electronic states. The gradually evolving spectral features can be accurately and feasibly simulated within nuclear ensemble methods and interpreted with the population analysis.

Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction.

Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0 eV.

Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane.

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

Resonant Auger decay of dissociating CH3I near the I 4d threshold.

Resonant Auger processes provide a unique perspective on electronic interactions and excited vibrational and electronic states of molecular ions. Here, new data are presented on the resonant Auger decay of excited CH3I in the region just below the I 4d-1 ionization threshold. The resonances include the Rydberg series converging to the five spin-orbit and ligand-field split CH3I (I 4d-1) thresholds, as well as resonances corresponding to excitation from the I 4d5/2,3/2 orbitals into the σ* lowest unoccupied molecular orbital. This study focuses on participator decay that populates the lowest lying states of CH3I+, in particular, the X̃2E3/2 and 2E1/2 states, and on spectator decay that populates the lowest-lying (CH3I2+)σ* states of CH3I+. The CH3I (I 4d-1)σ* resonances are broad, and dissociation to CH3 + I competes with the autoionization of the core-excited states. Auger decay as the molecule dissociates produces a photoelectron spectrum with a long progression (up to v3+ ∼ 25) in the C-I stretching mode of the X̃2E3/2 and 2E1/2 states, providing insights into the shape of the dissociative core-excited surface. The observed spectator decay processes indicate that CH3I+ is formed on the repulsive wall of the lower-lying (CH3I2+)σ* potentials, and the photon-energy dependence of the processes provides insights into the relative slopes of the (4d-1)σ* and (CH3I2+)σ* potential surfaces. Data are also presented for the spectator decay of higher lying CH3I (I 4d-1)nl Rydberg resonances. Photoelectron angular distributions for the resonant Auger processes provide additional information that helps distinguish these processes from the direct ionization signal.

Resonance between projected Tibetan Plateau surface darkening and Arctic climate change.

The Tibetan Plateau (TP) exerts a profound influence on global climate over million-year timescales due to its past uplift. However, whether the ongoing climate changes over the TP, particularly the persistent reduction in its local albedo (referred to as "TP surface darkening"), can exert global impacts remains elusive. In this study, a state-of-the-art coupled land-atmosphere global climate model has been employed to scrutinize the impact of TP darkening on polar climate changes. Results indicate that the projected TP darkening has the potential to generate a stationary Rossby wave train, thereby modulating the atmospheric circulation in the high-latitudes of the Northern Hemisphere and instigating a dipole-like surface air temperature anomaly pattern around the Arctic region. An additional experiment suggests that the projected Arctic warming may in return warm the TP, thus forming a bi-directional linkage between these two climate systems. Given their association with vast ice reservoirs, the elucidation of this mechanism in our study is crucial in advancing our comprehension of Earth system climate projections.

An evolutionarily distinct ringed seal in the Ilulissat Icefjord.

The Earth's polar regions are low rates of inter- and intraspecific diversification. An extreme mammalian example is the Arctic ringed seal (Pusa hispida hispida), which is assumed to be panmictic across its circumpolar Arctic range. Yet, local Inuit communities in Greenland and Canada recognize several regional variants; a finding supported by scientific studies of body size variation. It is however unclear whether this phenotypic variation reflects plasticity, morphs or distinct ecotypes. Here, we combine genomic, biologging and survey data, to document the existence of a unique ringed seal ecotype in the Ilulissat Icefjord (locally 'Kangia'), Greenland; a UNESCO World Heritage site, which is home to the most productive marine-terminating glacier in the Arctic. Genomic analyses reveal a divergence of Kangia ringed seals from other Arctic ringed seals about 240 kya, followed by secondary contact since the Last Glacial Maximum. Despite ongoing gene flow, multiple genomic regions appear under strong selection in Kangia ringed seals, including candidate genes associated with pelage coloration, growth and osmoregulation, potentially explaining the Kangia seal's phenotypic and behavioural uniqueness. The description of 'hidden' diversity and adaptations in yet another Arctic species merits a reassessment of the evolutionary processes that have shaped Arctic diversity and the traditional view of this region as an evolutionary freezer. Our study highlights the value of indigenous knowledge in guiding science and calls for efforts to identify distinct populations or ecotypes to understand how these might respond differently to environmental change.

Time-Resolved X-ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge.

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.

Southern Ocean warming and its climatic impacts.

The Southern Ocean has warmed substantially, and up to early 21st century, Antarctic stratospheric ozone depletion and increasing atmospheric CO2 have conspired to intensify Southern Ocean warming. Despite a projected ozone recovery, fluxes to the Southern Ocean of radiative heat and freshwater from enhanced precipitation and melting sea ice, ice shelves, and ice sheets are expected to increase, as is a Southern Ocean westerly poleward intensification. The warming has far-reaching climatic implications for melt of Antarctic ice shelf and ice sheet, sea level rise, and remote circulations such as the intertropical convergence zone and tropical ocean-atmosphere circulations, which affect extreme weathers, agriculture, and ecosystems. The surface warm and freshwater anomalies are advected northward by the mean circulation and deposited into the ocean interior with a zonal-mean maximum at ∼45°S. The increased momentum and buoyancy fluxes enhance the Southern Ocean circulation and water mass transformation, further increasing the heat uptake. Complex processes that operate but poorly understood include interactive ice shelves and ice sheets, oceanic eddies, tropical-polar interactions, and impact of the Southern Ocean response on the climate change forcing itself; in particular, limited observations and low resolution of climate models hinder rapid progress. Thus, projection of Southern Ocean warming will likely remain uncertain, but recent community effort has laid a solid foundation for substantial progress.

Suppressed basal melting in the eastern Thwaites Glacier grounding zone.

Thwaites Glacier is one of the fastest-changing ice-ocean systems in Antarctica1-3. Much of the ice sheet within the catchment of Thwaites Glacier is grounded below sea level on bedrock that deepens inland4, making it susceptible to rapid and irreversible ice loss that could raise the global sea level by more than half a metre2,3,5. The rate and extent of ice loss, and whether it proceeds irreversibly, are set by the ocean conditions and basal melting within the grounding-zone region where Thwaites Glacier first goes afloat3,6, both of which are largely unknown. Here we show-using observations from a hot-water-drilled access hole-that the grounding zone of Thwaites Eastern Ice Shelf (TEIS) is characterized by a warm and highly stable water column with temperatures substantially higher than the in situ freezing point. Despite these warm conditions, low current speeds and strong density stratification in the ice-ocean boundary layer actively restrict the vertical mixing of heat towards the ice base7,8, resulting in strongly suppressed basal melting. Our results demonstrate that the canonical model of ice-shelf basal melting used to generate sea-level projections cannot reproduce observed melt rates beneath this critically important glacier, and that rapid and possibly unstable grounding-line retreat may be associated with relatively modest basal melt rates.

Jahn-Teller effects in initial and final states: high-resolution X-ray absorption, photoelectron and Auger spectroscopy of allene.

Carbon K-edge resonant Auger spectra of gas-phase allene following excitation of the pre-edge 1s → π* transitions are presented and analysed with the support of EOM-CCSD/cc-pVTZ calculations. X-Ray absorption (XAS), X-ray photoelectron (XPS), valence band and non-resonant Auger spectra are also reanalysed with a series of computational approaches. The results presented demonstrate the importance of including nuclear ensemble effects for simulating X-ray observables and as an effective strategy for capturing Jahn-Teller effects in spectra.

Greenland Mass Trends From Airborne and Satellite Altimetry During 2011-2020.

We use satellite and airborne altimetry to estimate annual mass changes of the Greenland Ice Sheet. We estimate ice loss corresponding to a sea-level rise of 6.9 ± 0.4 mm from April 2011 to April 2020, with a highest annual ice loss rate of 1.4 mm/yr sea-level equivalent from April 2019 to April 2020. On a regional scale, our annual mass loss timeseries reveals 10-15 m/yr dynamic thickening at the terminus of Jakobshavn Isbræ from April 2016 to April 2018, followed by a return to dynamic thinning. We observe contrasting patterns of mass loss acceleration in different basins across the ice sheet and suggest that these spatiotemporal trends could be useful for calibrating and validating prognostic ice sheet models. In addition to resolving the spatial and temporal fingerprint of Greenland's recent ice loss, these mass loss grids are key for partitioning contemporary elastic vertical land motion from longer-term glacial isostatic adjustment (GIA) trends at GPS stations around the ice sheet. Our ice-loss product results in a significantly different GIA interpretation from a previous ice-loss product.

Auger electron angular distributions following excitation or ionization from the Xe 3d and F 1s levels in xenon difluoride.

Linearly polarized synchrotron radiation has been used to record polarization dependent, non-resonant Auger electron spectra of XeF2, encompassing the bands due to the xenon M45N1N45, M45N23N45, M45N45N45 and M45N45V and fluorine KVV transitions. Resonantly excited Auger spectra have been measured at photon energies coinciding with the Xe 3d5/2 → σ* and the overlapped Xe 3d3/2/F 1s → σ* excitations in XeF2. The non-resonant and resonantly excited spectra have enabled the Auger electron angular distributions, as characterized by the ßA parameter, to be determined for the M45N45N45 transitions. In the photon energy range over which the Auger electron angular distributions were measured, theoretical results indicate that transitions into the εf continuum channel dominate the Xe 3d photoionization in XeF2. In this limit, the theoretical value of the atomic alignment parameter (A20) characterizing the core ionized state becomes constant. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (α2) from the ßA parameters extracted from our non-resonant Auger spectra. For a particular Auger transition, the electron kinetic energy measured in the resonantly excited spectrum is higher than that in the directly ionized spectrum, due to the screening provided by the electron promoted into the σ* orbital. The interpretation of the F KVV Auger band in XeF2 has been discussed in relation to previously published one-site populations of the doubly charged ions (XeF22+). The experimental results show that the ionization energies of the doubly charged states predominantly populated in the decay of a vacancy in the F 1s orbital in XeF2 tend to be higher than those populated in the decay of a vacancy in the Xe 4d level in XeF2.

Vibronic interaction in trans-dichloroethene studied by vibration- and angle-resolved photoelectron spectroscopy using 19-90 eV photon energy.

Valence photoelectron spectra and photoelectron angular distributions of trans-dichloroethene have been measured with vibrational resolution at photon energies between 19 eV and 90 eV. Calculations of photoelectron anisotropy parameters, ß, and harmonic vibrational modes help provide initial insight into the molecular structure. The photon energy range encompasses the expected position of the atomic Cl 3p Cooper minimum. A corresponding dip observed here in the anisotropy of certain photoelectron bands permits the identification and characterization of those molecular orbitals that retain a localized atomic Cl character. The adiabatic approximation holds for the X2Au state photoelectron band, but vibronic coupling was inferred within the A-B-C and the D-E states by noting various failures of the Franck-Condon model, including vibrationally dependent ß-parameters. This is further explored using the linear vibronic coupling model with interaction parameters obtained from ab initio calculations. The A/B photoelectron band is appreciably affected by vibronic coupling, owing to the low-lying conical intersection of the A2Ag and B2Bu states. The C2Bg band is also affected, but to a lesser extent. The adiabatic minima of the D2Au and E2Ag states are almost degenerate, and the vibronic interaction between these states is considerable. The potential energy surface of the D2Au state is predicted to have a double-minimum shape with respect to the au deformations of the molecular structure. The irregular vibrational structure of the resulting single photoelectron band reflects the non-adiabatic nuclear dynamics occurring on the two coupled potential energy surfaces above the energy of their conical intersection.

Centennial response of Greenland's three largest outlet glaciers.

The Greenland Ice Sheet is the largest land ice contributor to sea level rise. This will continue in the future but at an uncertain rate and observational estimates are limited to the last few decades. Understanding the long-term glacier response to external forcing is key to improving projections. Here we use historical photographs to calculate ice loss from 1880-2012 for Jakobshavn, Helheim, and Kangerlussuaq glacier. We estimate ice loss corresponding to a sea level rise of 8.1 ± 1.1 millimetres from these three glaciers. Projections of mass loss for these glaciers, using the worst-case scenario, Representative Concentration Pathways 8.5, suggest a sea level contribution of 9.1-14.9 mm by 2100. RCP8.5 implies an additional global temperature increase of 3.7 °C by 2100, approximately four times larger than that which has taken place since 1880. We infer that projections forced by RCP8.5 underestimate glacier mass loss which could exceed this worst-case scenario.

Tracking the ultraviolet-induced photochemistry of thiophenone during and after ultrafast ring opening.

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S-C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

The Southern Ocean and its interaction with the Antarctic Ice Sheet.

The Southern Ocean exerts a major influence on the mass balance of the Antarctic Ice Sheet, either indirectly, by its influence on air temperatures and winds, or directly, mostly through its effects on ice shelves. How much melting the ocean causes depends on the temperature of the water, which in turn is controlled by the combination of the thermal structure of the surrounding ocean and local ocean circulation, which in turn is determined largely by winds and bathymetry. As climate warms and atmospheric circulation changes, there will be follow-on changes in the ocean circulation and temperature. These consequences will affect the pace of mass loss of the Antarctic Ice Sheet.

Ice Scallops: A Laboratory Investigation of the Ice-Water Interface.

Ice scallops are a small-scale (5-20cm) quasi-periodic ripple pattern that occurs at the ice-water interface. Previous work has suggested that scallops form due to a self-reinforcing interaction between an evolving ice-surface geometry, an adjacent turbulent flow field, and the resulting differential melt rates that occur along the interface. In this study, we perform a series of laboratory experiments in a refrigerated flume to quantitatively investigate the mechanisms of scallop formation and evolution in high resolution. Using particle-image velocimetry, we probe an evolving ice-water boundary layer at sub-millimeter scales and 15Hz frequency. Our data reveals three distinct regimes of ice-water interface evolution: A transition from flat to scalloped ice; an equilibrium scallop geometry; and an adjusting scallop interface. We find that scalloped ice geometry produces a clear modification to the ice-water boundary layer, characterized by a time-mean recirculating eddy feature that forms in the scallop trough. Our primary finding is that scallops form due to a self reinforcing feedback between the ice-interface geometry and shear production of turbulent kinetic energy in the flow interior. The length of this shear production zone is therefore hypothesized to set the scallop wavelength.

Rapid iceberg calving following removal of tightly packed pro-glacial mélange.

Iceberg calving is a major contributor to Greenland's ice mass loss. Pro-glacial mélange (a mixture of sea ice, icebergs, and snow) may be tightly packed in the long, narrow fjords that front many marine-terminating glaciers and can reduce calving by buttressing. However, data limitations have hampered a quantitative understanding. We develop a new radar-based approach to estimate time-varying elevations near the mélange-glacier interface, generating a factor of three or more improvement in elevation precision. We apply the technique to Jakobshavn Isbræ, Greenland's major outlet glacier. Over a one-month period in early summer 2016, the glacier experienced essentially no calving, and was buttressed by an unusually thick mélange wedge that increased in thickness towards the glacier front. The extent and thickness of the wedge gradually decreased, with large-scale calving starting once the mélange mass within 7 km of the glacier front had decreased by >40%.