We review the central concepts (e.g. conical intersections) of mechanistic non-adiabatic chemistry as well dynamics methods that can be used where more than one potential surface is involved. With the...
Solid Oxide Cell (SOC) technology is increasingly establishing itself globally as a mature technology for both power generation and green hydrogen production. In particular, Ceres’ metal supported SOC Endura platform,...
This study investigates the effect of ultrasound (US) on the electrochemical performance and two-phase flow regimes within a custom-designed polymer electrolyte membrane water electrolyser (PEMWE) cell. The electrolyser cell was...
Magnetohydrodynamic (MHD) effects in electrochemical systems offer promising routes to enhanced current densities by reducing ohmic resistance, in part through the removal of gas bubbles and froth accumulating at the...
Electrochemical CO₂ reduction offers a promising route for converting CO₂ into value-added fuels and chemicals using renewable electricity, but its practical implementation remains limited by CO₂ mass transport and non-uniform...
Binding energies of CO and H are determined using temperature programmed desorption of CO and H 2 from Pd(111), PdH/Pd(111), and Cu/PdH/Pd(111) under ultra-high vacuum conditions and are correlated with electrocatalytic selectivity.
This study demonstrates the utility of the electrochemical-surface force balance (e-SFB) for observing solid electrolyte interphase (SEI) formation directly at an electrode surface. Through proof-of-concept measurements of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) based electrolytes, absolute thickness and mechanical properties of SEIs are measured in situ before and after electrochemical cycling. The SEIs that formed in these systems were found to have thickness on the order of 100s of nm and elastic moduli on the order of 10s of MPa depending on cycling conditions and the nature of the solvent.
Electrochemical impedance spectroscopy (EIS) is widely used to probe the solid electrolyte interphase (SEI) in alkali-metal batteries, yet the interpretation of impedance responses remains challenging due to the simultaneous influence of interfacial transport properties and evolving electrode morphology. Here, we systematically evaluate the capability of EIS to characterise SEI behaviour in symmetric lithium- and sodium-metal cells using carbonate and ether electrolytes. Time-resolved impedance measurements were combined with distribution-of-relaxation-times analysis, equivalent-circuit modelling, temperature-dependent EIS, and in situ NMR spectroscopy to track interfacial evolution during formation, cycling, and rest. EIS captures key interfacial changes, including resistance growth during open-circuit conditions and capacitance increases associated with expansion of the electrochemically active surface area during cycling. However, comparison with in situ NMR reveals that continuous microstructure formation and SEI accumulation can occur without being directly reflected in impedance-derived SEI parameters. Temperature-dependent analysis further shows that activation energies derived from resistance may include geometric contributions associated with surface-area changes, whereas analysis of the interfacial time constant provides a more surface-area-independent metric of SEI transport. These results demonstrate that while EIS is a powerful tool for monitoring interfacial evolution, impedance responses in metal-electrode systems must be interpreted carefully and supported by complementary techniques to distinguish intrinsic SEI properties from morphology-driven effects.
The integration of CO2 capture and conversion into a single system has been suggested as an efficient and transformative approach for enabling the conversion of CO2 to high-value chemicals and...
The simulation of photochemical reactions requires a quantum mechanical treatment of electronic and nuclear dynamics. Most simulation approaches use the Born-Oppenheimer (BO) approximation and calculations of nonadiabatic couplings to evolve a wavefunction on a set of BO electronic states. However, the use of BO states present several challenges such as discontinuous surfaces, singular terms in the Hamiltonian, and double-valued boundary conditions. We present a direct dynamics approach for molecular vibronic dynamics which does not invoke the BO approximation simply by avoiding diagonalization of the electronic part of the Hamiltonian. By employing a diabatic propagation scheme for the orbitals, we ensure that all electronic terms vary smoothly as a function of nuclear coordinates in a basis of configuration state functions (CSFs). We derive equations of motion for mixed quantum-classical dynamics techniques employing averaged potentials, such that the simulated trajectories evolve on linear combinations of CSF surfaces. We test our approach for lithium hydride and ethylene. In contrast with BO electronic surfaces, we find that all CSF surfaces and couplings are smooth and integrable in the vicinity of conical intersections and weak avoided crossings. Comparisons of the dynamics of photoexcited lithium hydride show that Ehrenfest dynamics reproduce changes in electronic state populations, but lead to over-coherence. Our equations of motion for coupled-trajectory dynamics fail to reduce the over-coherence problem due to the reliance of the derivation on the BO approximation. With further work on the selection of orbitals and the mixed quantum-classical equations of motion, our work shows the potential of a pre-BO wavefunction ansatz for practical nonadiabatic dynamics simulations.
Catalytic activity and selectivity of 2-propanol dissociation is investigated over pristine and vanadium-oxide loaded Co3O4(111), forming acetone at low V loadings while increasing V coverage results in C–O bond scission and the formation of propene.
Capillary-fed electrolysis (CFE) offers a promising approach to achieving very high energy efficiency in alkaline water electrolysis by avoiding gas bubble formation and associated energy losses. In CFE cells, capillary-induced...
Electrochemical lithium-mediated nitrogen reduction (Li-NRR) has emerged as a leading approach for ammonia electrosynthesis under mild conditions, particularly in continuous flow-cell configurations. Despite the rapid progress of this strategy, as...
The Projected Forces and Momenta (PFM) decoherence correction has been recently introduced [J. Chem. Theory Comput. 2025, 21, 10645] and successfully applied for trajectory surface-hopping (TSH) simulations describing the coupled...
Quasi-solid-state lithium-sulfur batteries offer a promising route to combine the high energy density of lithium-sulfur chemistry with improved interfacial stability. However, their performance is limited by the formation of resistive solid-liquid electrolyte interphases at the interface between the solid electrolyte separator and the liquid catholyte. In this work, we investigate solid-liquid electrolyte interphase formation at the interface between an argyrodite-type sulfide solid electrolyte Li5.5PS4.5Cl1.5 and two representative liquid electrolytes: a conventional ether-based electrolyte (LiTFSI in DOL:DME) and an ionic liquid (LiTFSI in EMIMTFSI). Using a combination of time-resolved electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and focussed ion beam scanning electron microscopy, we reveal substantial differences in interphase chemistry, morphology, and transport properties. The ether-based electrolyte undergoes continuous chemical reaction with the sulfide solid electrolyte, forming a thick, inhomogeneous, and highly resistive interphase (∼2000 Ω cm2 after 250 h), driven in part by dissolution of polysulfide species. In contrast, the ionic liquid electrolyte forms a significantly thinner, layered interphase with a comparatively low area-specific resistance (∼150-220 Ω cm2), which remains constant over extended time and during electrochemical cycling. These findings demonstrate that choice of catholyte plays an important role in governing solid-liquid electrolyte interphase formation, and highlights ionic liquids as viable catholytes for stable, low-resistance interfaces in quasi-solid-state lithium-sulfur batteries with argyrodite-type solid electrolyte separators.
Stable, earth-abundant catalysts for the oxygen evolution reaction (OER), which is a bottleneck in water electrolysis, operating in neutral media, are essential for advancing environmentally friendly water electrolysis and CO2...
In a backdrop of energy transition and geopolitical tensions, efficient biomass-assisted hydrogen production with non-platinum group metals is sought out. Understanding of the related reaction mechanisms is crucial for the...
Coulometric titration time analysis (CTTA) has recently emerged as a powerful technique for quantifying the rate of solid electrolyte interphase (SEI) growth and elucidating the underlying mechanisms governing degradation in solid-state batteries with argyrodite solid electrolytes. However, subsequent studies employing metallic interlayers and variable stack pressures have revealed that CTTA results are highly sensitive to the effective contact area between the solid electrolyte and the current collector. In this work, we further explore CTTA as a SEI characterisation technique to gain more information on its strengths and weaknesses. The findings highlight key challenges when comparing results across samples and propose strategies to mitigate these effects. Moreover, this study contextualises CTTA within the broader suite of SEI characterisation techniques, offering guidance on its optimal implementation and interpretation.
