Exploring non-adiabaticity to CO reduction reaction through ab initio molecular dynamics simulation

Non-adiabatic chemical reaction refers to the electronic excitation during reactions. This effect cannot be modeled by the ground-state Born-Oppenheimer molecular dynamics (BO-MD), where the electronic structure is at the ground state for every step of ions' movement. Although the non-adiabatic effect has been explored extensively in gas phase reactions, its role in electrochemical reactions, such as water splitting and CO2 reduction, in electrolyte has been rarely explored. On the other hand, electrochemical reactions usually involve electron transport; thus, a non-adiabatic process can naturally play a significant role. In this work, using one-step CO2 reduction as an example, we investigated the role of the non-adiabatic effect in the reaction. The reaction barriers were computed by adiabatic BO-MD and non-adiabatic real-time time dependent density functional theory (rt-TDDFT). We found that by including the non-adiabatic effect, rt-TDDFT could increase the reaction barrier up to 6% compared to the BO-MD calculated barrier when the solvent model is used to represent water. Simulations were carried out using explicit water molecules around the reaction site under different overpotentials, and similar non-adiabatic effects were found

Signal detection for non-orthogonal space-time block coding over time-selective fading channels

In the case of non-quasi-static (i.e., time-selective fast fading) channels, which do exist in practice, the performance of the existing NO-STBC detectors can suffer from an irreducible error floor. To this end, this letter proposes a zero-forcing-based signal detector, which is not only computationally simple but also highly effective in mitigating the impact of channel variation on system performance

Discrete dislocation and crystal plasticity analyses of load shedding in polycrystalline titanium alloys

The focus of this paper is the mechanistic basis of the load shedding phenomenon that occurs under the dwell fatigue loading scenario. A systematic study was carried out using a discrete dislocation plasticity (DDP) model to investigate the effect of crystallographic orientations, localised dislocation behaviour and grain combinations on the phenomenon. Rate sensitivity in the model arises from a thermal activation process at low strain rates, which is accounted for by associating a stress- and temperature-dependent release time with obstacles; the activation energy was determined by calibrating an equivalent crystal plasticity model to experimental data. First, the application of Stroh's dislocation pile-up model of crack nucleation to facet fracture was quantitatively assessed using the DDP model. Then a polycrystalline model with grains generated using a controlled Poisson Voronoi tessellation was used to investigate the soft-hard-soft rogue grain combination commonly associated with load shedding. Dislocation density and peak stress at the soft/hard grain boundary increased significantly during the stress dwell period, effects that were enhanced by dislocations escaping from pile-ups at obstacles. The residual stress after dwell fatigue loading was also found to be much higher compared to standard fatigue loading. Taylor (uniform strain) and Sachs (uniform stress) type assumptions in a soft-hard grain combination have been assessed with a simple bicrystal DDP model. Basal slip nucleation in the hard grain was found to be initiated by high stresses generated by strong pile ups in the soft grain, and both basal and pyramidal slip nucleation was observed in the hard grain when the grain boundary orientation aligned with that of an active slip system in the soft grain. The findings of this study give new insight into the mechanisms of load shedding and faceting associated with cold dwell fatigue in Ti alloys used in aircraft engines

Investigation of slip transfer across HCP grain boundaries with application to cold dwell facet fatigue

This paper addresses the role of grain boundary slip transfer and thermally-activated discrete dislocation plasticity in the redistribution of grain boundary stresses during cold dwell fatigue in titanium alloys. Atomistic simulations have been utilised to calculate the grain boundary energies for titanium with respect to the misorientation angles. The grain boundary energies are utilised within a thermally-activated discrete dislocation plasticity model incorporating slip transfer controlled by energetic and grain boundary geometrical criteria. The model predicts the grain size effect on the flow strength in Ti alloys. Cold dwell fatigue behaviour in Ti-6242 alloy is investigated and it is shown that significant stress redistribution from soft to hard grains occurs during the stress dwell, which is observed both for grain boundaries for which slip transfer is permitted and inhibited. However, the grain boundary slip penetration is shown to lead to significantly higher hard-grain basal stresses near the grain boundary after dwell, thus exacerbating the load shedding stress compared to an impenetrable grain boundary. The key property controlling the dwell fatigue response is argued to remain the time constant associated with the thermal activation process for dislocation escape, but the slip penetrability is also important and exacerbates the load shedding. The inclusion of a macrozone does not significantly change the conclusions but does potentially lead to the possibility of a larger initial facet

Signal detection for orthogonal space-time block coding over time-selective fading channels: A PIC approach for the G(i) systems

One major assumption in all orthogonal space-time block coding (O-STBC) schemes is that the channel remains static over the entire length of the codeword. However, time selective fading channels do exist, and in such case the conventional O-STBC detectors can suffer from a large error floor in the high signal-to-noise ratio (SNR) cases. This paper addresses such an issue by introducing a parallel interference cancellation (PIC) based detector for the G(i) coded systems (i = 3 and 4)

Particle-hole symmetry and interaction effects in the Kane-Mele-Hubbard model

We prove that the Kane-Mele-Hubbard model with purely imaginary next-nearest-neighbor hoppings has a particle-hole symmetry at half-filling. Such a symmetry has interesting consequences including the absence of charge and spin currents along open edges, and the absence of the sign problem in the determinant quantum Monte-Carlo simulations. Consequentially, the interplay between band topology and strong correlations can be studied at high numeric precisions. The process that the topological band insulator evolves into the antiferromagnetic Mott insulator as increasing interaction strength is studied by calculating both the bulk and edge electronic properties. In agreement with previous theory analyses, the numeric simulations show that the Kane-Mele-Hubbard model exhibits three phases as increasing correlation effects: the topological band insulating phase with stable helical edges, the bulk paramagnetic phase with unstable edges, and the bulk antiferromagnetic phase