The plausibility of claimed induced seismicity.

Claims of industrially induced seismicity vary from indisputable to unpersuasive and yet the veracity of industrial induction is vital for regulatory and operational practice. Assessment schemes have been developed in response to this need. We report here an initial assessment of the reliability of all globally known cases of proposed human-induced earthquakes and invite specialists on particular cases to refine these results.

Microdroplets initiate organic-inorganic interactions and mass transfer in thermal hydrous geosystems.

Organic-inorganic interactions regulate the dynamics of hydrocarbons, water, minerals, CO, and H in thermal rocks, yet their initiation remains debated. To address this, we conducted isotope-tagged and in-situ visual thermal experiments. Isotope-tagged studies revealed extensive H/O transfers in hydrous n-CH-HO-feldspar systems.

Primary N-He gas field formation in intracratonic sedimentary basins.

Helium, nitrogen and hydrogen are continually generated within the deep continental crust. Conceptual degassing models for quiescent continental crust are dominated by an assumption that these gases are dissolved in water, and that vertical transport in shallower sedimentary systems is by diffusion within water-filled pore space (for example, refs. ).

Atmospheric muography for imaging and monitoring tropic cyclones.

Large-scale solid bodies on Earth such as volcanoes and man-made pyramids have been visualized with solid earth muography, and the recently invented technique, acqueous muography, has already demonstrated its capability to visualize ocean tides and tsunami. In this work, atmospheric muography, a technique to visualize and monitor the vertical profile of tropic cyclones (TCs) is presented for the first time. The density distribution and time-dependent behavior of several TCs which had approached Kagoshima, Japan, has been investigated with muography.

The Use of Bridging Ligand Substituents to Bias the Population of Localized and Delocalized Mixed-Valence Conformers in Solution.

The electronic structure and associated spectroscopic properties of ligand-bridged, bimetallic 'mixed-valence' complexes of the general form {M}(μ-B){M } are dictated by the electronic couplings, and hence orbital overlaps, between the metal centers mediated by the bridge. In the case of complexes such as [{Cp*(dppe)Ru}(μ-C≡CC H C≡C){Ru(dppe)Cp*}] , the low barrier to rotation of the half-sandwich metal fragments and the arylene bridge around the acetylene moieties results in population of many energy minima across the conformational energy landscape. Since orbital overlap is also sensitive to the particular mutual orientations of the metal fragment(s) and arylene bridge through a Karplus-like relationship, the different members of the population range exemplify electronic structures ranging from strongly localized (weakly coupled Robin-Day Class II) to completely delocalized (Robin-Day Class III).

Periodic sea-level oscillation in Tokyo Bay detected with the Tokyo-Bay seafloor hyper-kilometric submarine deep detector (TS-HKMSDD).

Meteorological-tsunami-like (or meteotsunami-like) periodic oscillation was muographically detected with the Tokyo-Bay Seafloor Hyper-Kilometric Submarine Deep Detector (TS-HKMSDD) deployed in the underwater highway called the Trans-Tokyo Bay Expressway or Tokyo Bay Aqua-Line (TBAL). It was detected right after the arrival of the 2021 Typhoon-16 that passed through the region 400 km south of the bay. The measured oscillation period and decay time were respectively 3 h and 10 h.

A Spectroscopic and Computationally Minimal Approach to the Analysis of Charge-Transfer Processes in Conformationally Fluxional Mixed-Valence and Heterobimetallic Complexes.

Class II mixed-valence bimetallic complexes {[Cp'(PP)M]C≡C-C≡N[M'(PP)'Cp']} (M, M'=Ru, Fe; PP=dppe, (PPh ) ; Cp'=Cp*, Cp) exist as conformational ensembles in fluid solution, with a population of structures ranging from cis- to trans-like geometries. Each conformer gives rise to its own series of low-energy intervalence charge-transfer (IVCT) and local d-d transitions, which overlap in the NIR region, giving complex band envelopes in the NIR absorption spectrum, which prevent any meaningful attempt at analysis of the band shape. However, DFT and time-dependent (TD)DFT calculations with dispersion-corrected global-hybrid (BLYP35-D3) or local hybrid (lh-SsirPW92-D3) functionals on a small number of optimised structures chosen to sample the ground state potential energy hypersurfaces of each of these complexes has proven sufficient to explain the major features of the electronic spectra.

Passive, continuous monitoring of carbon dioxide geostorage using muon tomography.

Carbon capture and storage is a transition technology from a past and present fuelled by coal, oil and gas and a planned future dominated by renewable energy sources. The technology involves the capture of carbon dioxide emissions from fossil fuel power stations and other point sources, compression of the CO into a fluid, transporting it and injecting it deep beneath the Earth's surface into depleted petroleum reservoirs and other porous formations. Once injected, the CO must be monitored to ensure that it is emplaced and assimilated as planned and that none leaks back to surface.

The potential for spills and leaks of contaminated liquids from shale gas developments.

Rapid growth of hydraulic fracturing for shale gas within the USA and the possibility of shale developments within Europe has created public concern about the risks of spills and leaks associated with the industry. Reports from the Texas Railroad Commission (1999 to 2015) and the Colorado Oil and Gas Commission (2009 to 2015) were used to examine spill rates from oil and gas well pads. Pollution incident records for England and road transport incident data for the UK were examined as an analogue for potential offsite spills associated with transport for a developing shale industry.

An assessment of the footprint and carrying capacity of oil and gas well sites: The implications for limiting hydrocarbon reserves.

We estimate the likely physical footprint of well pads if shale gas or oil developments were to go forward in Europe and used these estimates to understand their impact upon existing infrastructure (e.g. roads, buildings), the carrying capacity of the environment, and how the proportion of extractable resources maybe limited.

Sandwich and half-sandwich metal complexes derived from cross-conjugated 3-methylene-penta-1,4-diynes.

The cross-conjugated ethynyl-vinylidene [PhC[double bond, length as m-dash]C(C[triple bond, length as m-dash]CH){C(H)[double bond, length as m-dash]CRu(PPh)Cp}]PF ([4a]PF), and [FcC(H)[double bond, length as m-dash]C(C[triple bond, length as m-dash]CH){C(H)[double bond, length as m-dash]CRu(PPh)Cp}]PF ([4b]PF), and ethynyl-alkynyl PhC[double bond, length as m-dash]C(C[triple bond, length as m-dash]CH){C[triple bond, length as m-dash]CRu(PPh)Cp} (5a), and FcC(H)[double bond, length as m-dash]C(C[triple bond, length as m-dash]CH){C[triple bond, length as m-dash]CRu(PPh)Cp} (5b) compounds (Cp = η-cyclopentadienyl) have been prepared from reactions of the known 3-methylene-penta-1,4-diynes PhC[double bond, length as m-dash]C(C[triple bond, length as m-dash]CH) (3a) and [FcCH[double bond, length as m-dash]C(C[triple bond, length as m-dash]CH)] (3b) with [RuCl(PPh)Cp]. The compounds derived from 3b incorporating the more electron-rich alkene proved to be unstable during work-up, and attempts to prepare bis(ruthenium) complexes from 3a and 3b or from transmetallation reactions of the bis(alkynylgold) complex FcCH[double bond, length as m-dash]C(C[triple bond, length as m-dash]CAuPPh) (7) with RuCl(PPh)Cp were unsuccessful. The related bis- and tris(ferrocenyl) derivatives PhC[double bond, length as m-dash]C(C[triple bond, length as m-dash]CFc) (6a) and FcCH[double bond, length as m-dash]C(C[triple bond, length as m-dash]CFc) (6b) were more readily obtained from Pd(ii)/Cu(i) catalysed cross-coupling reactions of FcC[triple bond, length as m-dash]CH with the 1,1-dibromo vinyl complexes PhC[double bond, length as m-dash]CBr (1a) and FcC(H)[double bond, length as m-dash]CBr (1b).

Rational Control of Conformational Distributions and Mixed-Valence Characteristics in Diruthenium Complexes.

The electronic characteristics of mixed-valence complexes are often inferred from the shape of the inter-valence charge transfer (IVCT) band, which usually falls in the near infrared (NIR) region, and relationships derived from Marcus-Hush theory. These analyses typically assume one single, dominant molecular conformation. The NIR spectra of the prototypical delocalised (Class III Robin-Day mixed-valence) complexes [{Ru(pp)Cp'} (μ-C≡C-C≡C)] ([1] : Cp'=Cp, pp=(PPh ) ; [2] : Cp'=Cp, pp=dppe; [3] : Cp'=Cp*, pp=dppe) feature a 'two-band' pattern, which complicates band-shape analysis using these traditional methods.

Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations.

A series of cross-conjugated compounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1-6) have been synthesized. The linear optical absorption properties can be tuned by modification of the substituents at the 1 and 5 positions of the hexa-3-en-1,5-diynyl backbone (1: Si(CH(CH3)2)3, 2: C6H4C≡CSi(CH3)3, 3: C6H4COOCH3, 4: C6H4CF3, 5: C6H4C≡N, 6: C6H4C≡CC5H4N), although attempts to introduce electron-donating (C6H4CH3, C6H4OCH3, C6H4Si(CH3)3) substituents at these positions were hampered by the ensuing decreased stability of the compounds. Spectroelectrochemical investigations of selected examples, supported by DFT-based computational studies, have shown that one- and two-electron oxidation of the 1,2-bis(triarylamine)ethene fragment also results in electronic changes to the perpendicular π-system in the hexa-3-en-1,5-diynyl branch of the molecule.

Electrochemical Single-Molecule Transistors with Optimized Gate Coupling.

Electrochemical gating at the single molecule level of viologen molecular bridges in ionic liquids is examined. Contrary to previous data recorded in aqueous electrolytes, a clear and sharp peak in the single molecule conductance versus electrochemical potential data is obtained in ionic liquids. These data are rationalized in terms of a two-step electrochemical model for charge transport across the redox bridge.

Impact of Maximum Allowable Cost on CO2 Storage Capacity in Saline Formations.

Injecting CO2 into deep saline formations represents an important component of many greenhouse-gas-reduction strategies for the future. A number of authors have posed concern over the thousands of injection wells likely to be needed. However, a more important criterion than the number of wells is whether the total cost of storing the CO2 is market-bearable.

Mixed-valence ruthenium complexes rotating through a conformational Robin-Day continuum.

The conformational energy landscape and the associated electronic structure and spectroscopic properties (UV/Vis/near-infrared (NIR) and IR) of three formally d(5)/d(6) mixed-valence diruthenium complex cations, [{Ru(dppe)Cp*}2(μ-C≡CC6H4C≡C)](+), [1](+), [trans-{RuCl(dppe)2}2(μ-C≡CC6H4C≡C)](+), [2](+), and the Creutz-Taube ion, [{Ru(NH3)5}2(μ-pz)](5+), [3](5+) (Cp = cyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; pz = pyrazine), have been studied using a nonstandard hybrid density functional BLYP35 with 35 % exact exchange and continuum solvent models. For the closely related monocations [1](+) and [2](+), the calculations indicated that the lowest-energy conformers exhibited delocalized electronic structures (or class III mixed-valence character). However, these minima alone explained neither the presence of shoulder(s) in the NIR absorption envelope nor the presence of features in the observed vibrational spectra characteristic of both delocalized and valence-trapped electronic structures.

Long range charge transfer in trimetallic mixed-valence iron complexes mediated by redox non-innocent cyanoacetylide ligands.

The reaction of Fe(C≡CC≡N)(dppe)Cp (1) with one-half equivalent of [trans-Fe(N≡CMe)2(dppx)2][BF4]2 (dppx = dppe ([2][BF4]2) or dppm ([3][BF4]2)) affords trimetallic [trans-Fe{N≡CC≡CFe(dppe)Cp}2(dppx)2][BF4]2 (dppx = dppe [4][BF4]2; dppx = dppm [5][BF4]2). Both [4][BF4]2 and [5][BF4]2 undergo three, one-electron oxidation processes, arising from sequential oxidation of the two terminal Fe(C≡CR)(dppe)Cp moieties and finally the central Fe(N≡CR)2(dppx)2 fragment. The redox products [4](n+) and [5](n+) (n = 3, 4) have been characterised by UV-vis-NIR and IR spectroelectrochemistry.

Refining the interpretation of near-infrared band shapes in a polyynediyl molecular wire.

Spinning to improve (band) shape: A blend of theoretical and experimental work demonstrates that the rotational conformation of mixed-valence complexes influences the low-energy (NIR) transitions in such molecules. Interpretations of the NIR band shapes are presented.

Disila-analogues of the synthetic retinoids EC23 and TTNN: synthesis, structure and biological evaluation.

Silicon chemistry offers the potential to tune the effects of biologically active organic molecules. Subtle changes in the molecular backbone caused by the exchange of a carbon atom for a silicon atom (sila-substitution) can significantly alter the biological properties. In this study, the biological effects of a two-fold sila-substitution in the synthetic retinoids EC23 (4-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-ylethynyl)benzoic acid (4a)) and TTNN (6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-naphthoic acid (7a)) as well as their corresponding analogues with an indane instead of a 1,2,3,4-tetrahydronaphthalene skeleton (compounds 5a and 8a) were investigated.