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

Wannier–Koopmans method calculations for transition metal oxide band gaps

The widely used density functional theory (DFT) has a major drawback of underestimating the band gaps of materials. Wannier–Koopmans method (WKM) was recently developed for band gap calculations with accuracy on a par with more complicated methods. WKM has been tested for main group covalent semiconductors, alkali halides, 2D materials, and organic crystals. Here we apply the WKM to another interesting type of material system: the transition metal (TM) oxides. TM oxides can be classified as either with d0 or d10 closed shell occupancy or partially occupied open shell configuration, and the latter is known to be strongly correlated Mott insulators. We found that, while WKM provides adequate band gaps for the d0 and d10 TM oxides, it fails to provide correct band gaps for the group with partially occupied d states. This issue is also found in other mean-field approaches like the GW calculations. We believe that the problem comes from a strong interaction between the occupied and unoccupied d-state Wannier functions in a partially occupied d-state system. We also found that, for pseudopotential calculations including deep core levels, it is necessary to remove the electron densities of these deep core levels in the Hartree and exchange–correlation energy functional when calculating the WKM correction parameters for the d-state Wannier functions

Anharmonic multi-phonon nonradiative transition: An ab initio calculation approach

Nonradiative carrier recombinations at deep centers in semiconductors are of great importance for both fundamental physics and device engineering. In this article, we provide a revised analysis of Huang’s original nonradiative multi-phonon (NMP) theory with ab initio calculations. First, we confirmed at the first-principles level that Huang’s concise formula gives the same results as the matrix-based formula, and that Huang’s high-temperature formula provides an analytical expression for the coupling constant in Marcus theory. Secondly, we correct for anharmonic effects by taking into account local phonon-mode variations for different charge states of a defect. The corrected capture rates for defects in GaN and SiC agree well with experiments

First-principles Green-Kubo method for thermal conductivity calculations

We present a first-principles approach to calculate the phonon thermal conductivity based on the Green-Kubo formalism. In this approach, the density functional theory energy is distributed to each atom, and a two-step method in the molecular dynamics is introduced to avoid the atomic position R wrapping problem in a periodic system when the heat current is calculated. We show that this first-principles Green-Kubo approach is particularly suitable for disordered systems like amorphous and liquid, where the thermal conductivities are small due to strong phonon scattering but difficult to be calculated using anharmonic interaction energy. We have applied our method to liquid Ar, liquid Si, and amorphous Si. The calculated thermal conductivities agree well with previous theoretical and experimental results. We have also compared our method to previous works combining first-principles simulations with the Green-Kubo formalism

Nonadiabatic molecular dynamics with decoherence and detailed balance under a density matrix ensemble formalism

The mixed quantum-classical nonadiabatic molecular dynamics (NAMD) is a powerful tool to study many phenomena, especially ultrafast carrier transport and cooling. Carrier decoherence and detailed balance are two major issues in NAMD. So far, there is no computationally inexpensive approach to incorporate both effects. While the decoherence effect can be easily included in the state density matrix formalism and the detailed balance can be included in surface hopping or the wave function collapse approach, it is difficult to include both of them in a unified formalism. In this work we introduce a state density matrix formalism (referred to as P-matrix) including both the decoherence and detailed balance effects for NAMD. This method is able to explicitly treat the decoherence between different pairs of adiabatic states. Moreover, the off-diagonal density matrix elements are divided into two parts, corresponding to energy-increasing and energy-decreasing transitions. The detailed balance is then enforced by a Boltzmann factor applied to the energy-increasing transition part. The P-matrix formalism is applied to study hot-hole cooling and transfer processes in Si quantum dot (QD) systems. The calculated hot-carrier relaxation time is consistent with experiments. In a QD-pair system, the hot-hole cooling time shows weak dependence on the QD spacing. However, the hot-carrier transfer rate from one QD to another is found to decrease exponentially with the QD-QD distance. When the QD spacing is small (∼1 nm), the hot-carrier transfer can be very efficient. It is also shown that the explicit treatment of decoherence time is important in order to treat this hot-carrier transfer correctly

Large polaron formation and its effect on electron transport in hybrid perovskites

Many experiments have indicated that a large polaron may be formed in hybrid perovskites, and its existence is proposed to screen the carrier-carrier and carrier-defect scattering, thus contributing to the long lifetime of the carriers. However, a detailed theoretical study of the large polaron and its effect on carrier transport at the atomic level is still lacking. In particular, how strong is the large polaron binding energy? How does its effect compare with the effect of dynamic disorder caused by the A-site molecular rotation? And how does the inorganic sublattice vibration impact the motion of the large polaron? All of these questions are largely unanswered. In this work, using CH3NH3PbI3 as an example, we implement a tight-binding model fitted from density-functional theory to describe the electron large polaron ground state and to understand the large polaron formation and transport at its strong-coupling limit. We find that the formation energy of the large polaron is around -12 meV for the case without dynamic disorder, and -55 meV by including dynamic disorder. By performing the explicit time-dependent wavefunction evolution of the polaron state, together with the rotations of CH3NH3+ and vibrations of the PbI3- sublattice, we studied the diffusion constant and mobility of the large polaron state driven by the dynamic disorder and the sublattice vibration. Two effects of the inorganic sublattice vibrations are found: on one hand, the vibration of the sublattice provides an additional driving force for carrier mobility; on the other hand, the large polaron polarization further localizes the electron, reducing its mobility. Overall, the effect of the large polaron is to slow down the electron mobility by roughly a factor of two. We believe that both dynamic disorder due to rotation of the organic molecule, and large polaron effects induced by the polarization and vibration of the inorganic sublattice, play important roles for the electronic structure and carrier dynamics of the system

Solid 3D Li-S Battery Design via Stacking 2D Conductive Microporous Coordination Polymers and Amorphous Li-S Layers

To make a lithium-sulfur (Li-S) battery practical, not only high gravimetric energy capacity is important, but also high volumetric energy capacity will be required. The currently explored Li-S cathode designs often deploy systems with liquid electrolyte infiltration, hence with relatively low volumetric capacity. In the current study, we theoretically test a compact solid three-dimensional (3D) design (more like a Li-ion battery cathode than a conventional Li-S cathode) consisted of a sandwich structure alternating between the two-dimensional (2D) Mn-hexaaminobenzene-based coordination polymer (2D Mn-HAB-CP) layer and the amorphous Li-S layer. We study the theoretical limits for both its gravimetric and volumetric energy capacity, as well as its structural stability and Li diffusion within the cathode system. To study the Li diffusion within an amorphous system, we also develop a pull-atom molecular dynamics (PA-MD) to calculate the barrier heights of such disordered systems. We reveal the mechanism that determines the Li diffusion in the amorphous layer of the system. Overall, we find such a 3D solid Li-S cathode can be practical, with sufficient large gravimetric and volumetric energy capacity, as well as the Li diffusion constant. It also solves many other common Li-S cathode problems, from Li polysulfide dissolution to electrical insulating, and structure instabilities

Nanoimaging of Organic Charge Retention Effects: Implications for Nonvolatile Memory, Neuromorphic Computing, and High Dielectric Breakdown Devices

While a large variety of organic and molecular materials have been found to exhibit charge memory effects, the underlying mechanism is not well-understood, which hinders rational device design. Here, we study the charge retention mechanism of a nanoscale memory system, an organic monolayer on a silicon substrate, with Au nanoparticles on top serving as the electrical contact. Combining scanning probe imaging/manipulation and density functional simulations, we observe stable charge retention effects in the system and attributed it to polaron effects at the amine functional groups. Our findings can pave the way for applications in nonvolatile memory, neuromorphic computing, and high dielectric breakdown devices

The cultivation, bioactive components and pharmacological effects of Armillaria mellea

Armillaria mellea, a symbiotic fungus in the underground tubers of Chinese medicinal orchid Gastrodia elata, is one of the main biological active components and pharmaceutical effects of its host gastrodia. The purpose of this review is to bring attention to the biological properties of this unique A. mellea mushroom and its constituents, as well as to suggest the potential for the development of new drugs related to this fungus. It contains various known and untapped bioactive metabolites such aspolysaccharides, sesquiterpene aryl esters, steroids and fibrinolytic enzymes. It could be exploited as an important source of new biological natural products with anticonvulsant, immunomodulatory andantimicrobial functions. The batch culture is preferred as an alternative means of getting bioactive components from Armellaria fermentation. Challenges in investigations on A. mellea include the optimization of culture parameters, the further elucidation of the molecular pharmacological mechanism and relationship between structure and function of their secondary metabolites

Itinerant ferromagnetism and intrinsic anomalous Hall effect in amorphous iron-germanium

The amorphous iron-germanium system (a-FexGe1-x) lacks long-range structural order and hence lacks a meaningful Brillouin zone. The magnetization of a-FexGe1-x is well explained by the Stoner model for Fe concentrations x above the onset of magnetic order around x=0.4, indicating that the local order of the amorphous structure preserves the spin-split density of states of the Fe-3d states sufficiently to polarize the electronic structure despite k being a bad quantum number. Measurements reveal an enhanced anomalous Hall resistivity ρxyAH relative to crystalline FeGe; this ρxyAH is compared to density-functional theory calculations of the anomalous Hall conductivity to resolve its underlying mechanisms. The intrinsic mechanism, typically understood as the Berry curvature integrated over occupied k states but shown here to be equivalent to the density of curvature integrated over occupied energies in aperiodic materials, dominates the anomalous Hall conductivity of a-FexGe1-x (0.38≤x≤0.61). The density of curvature is the sum of spin-orbit correlations of local orbital states and can hence be calculated with no reference to k space. This result and the accompanying Stoner-like model for the intrinsic anomalous Hall conductivity establish a unified understanding of the underlying physics of the anomalous Hall effect in both crystalline and disordered systems