Correlated electron-nuclear dynamics of photoinduced water dissociation on rutile TiO2.

Elucidating the mechanism of photoinduced water splitting on TiO2 is important for advancing the understanding of photocatalysis and the ability to control photocatalytic surface reactions. However, incomplete experimental information and complex coupled electron-nuclear motion make the microscopic understanding challenging. Here we analyse the atomic-scale pathways of photogenerated charge carrier transport and photoinduced water dissociation at the prototypical water-rutile TiO2(110) interface using first-principles dynamics simulations. Two distinct mechanisms are observed. Field-initiated electron migration leads to adsorbed water dissociation via proton transfer to a surface bridging oxygen. In the other pathway, adsorbed water dissociation occurs via proton donation to a second-layer water molecule coupled to photoexcited-hole transfer promoted by in-plane surface lattice distortions. Two stages of non-adiabatic in-plane lattice motion-expansion and recovery-are observed, which are closely associated with population changes in Ti3d orbitals. Controlling such highly correlated electron-nuclear dynamics may provide opportunities for boosting the performance of photocatalytic materials.

Why Does Single-Atom Photocatalysis Work Better Than Conventional Photocatalysis? A Study on Ultrafast Excited Carrier and Structure Dynamics.

With the introduction of single atoms in photocatalysis, a small change in the electronic and geometric structure of the substrate can result in higher energy conversion efficiency, whereas the underlying microscopic dynamics are rarely illustrated. Here, employing real-time time-dependent density functional theory, we explore the ultrafast electronic and structural dynamics of single-atom photocatalysts (SAPCs) in water splitting at the microscopic scale. The results demonstrate that a single-atom Pt loaded on graphitic carbon nitride greatly promotes photogenerated carriers compared to traditional photocatalysts, and effectively separates the excited electrons from holes, prolonging the lifetime of the excited carriers. The flexible oxidation state (Pt2+, Pt0, or Pt3+) renders the single atom as an active site to adsorb the reactant and to catalyze the reactions as a charge transfer bridge at different stages during the photoreaction process. Our results offer deep insights into the single-atom photocatalytic reactions and benefit the design of high-efficiency SAPCs.

Ring Polymer Molecular Dynamics with Electronic Transitions.

Full quantum dynamics of molecules and materials is of fundamental importance, which requires a faithful description of simultaneous quantum motions of the electron and nuclei. A new scheme is developed for nonadiabatic simulations of coupled electron-nuclear quantum dynamics with electronic transitions based on the Ehrenfest theorem and ring polymer molecular dynamics. Built upon the isomorphic ring polymer Hamiltonian, time-dependent multistate electronic Schrödinger equations are solved self-consistently with approximate equation of motions for nuclei. Each bead bears a distinct electronic configuration and thus moves on a specific effective potential. This independent-bead approach provides an accurate description of the real-time electronic population and quantum nuclear trajectory, maintaining a good agreement with the exact quantum solution. Implementation of first-principles calculations enables us to simulate photoinduced proton transfer in H_{2}O-H_{2}O^{+} where we find a good agreement with experiment.

Optical Control of Multistage Phase Transition via Phonon Coupling in MoTe_{2}.

The temporal characters of laser-driven phase transition from 2H to 1T^{'} has been investigated in the prototype MoTe_{2} monolayer. This process is found to be induced by fundamental electron-phonon interactions, with an unexpected phonon excitation and coupling pathway closely related to the nonequilibrium relaxation of photoexcited electrons. The order-to-order phase transformation is dissected into three substages, involving energy and momentum scattering processes from optical (A_{1}^{'} and E^{'}) to acoustic phonon modes [LA(M)] in subpicosecond timescale. An intermediate metallic state along the nonadiabatic transition pathway is also identified. These results have profound implications on nonequilibrium phase engineering strategies.

Nonadiabatic Dynamics of Photocatalytic Water Splitting on A Polymeric Semiconductor.

To elucidate the nature of light-driven photocatalytic water splitting, a polymeric semiconductor-graphitic carbon nitride (g-C3N4)-has been chosen as a prototype substrate for studying atomistic water spitting processes in realistic environments. Our nonadiabatic quantum dynamics simulations based on real-time time-dependent density functional theory reveal explicitly the transport channel of photogenerated charge carriers at the g-C3N4/water interface, which shows a strong correlation to bond re-forming. A three-step photoreaction mechanism is proposed, whereas the key roles of hole-driven hydrogen transfer and interfacial water configurations were identified. Immediately following photocatalytic water splitting, atomic pathways for the two dissociated hydrogen atoms approaching each other and forming the H2 gas molecule are demonstrated, while the remanent OH radicals may form intermediate products (e.g., H2O2). These results provide critical new insights for the characterization and further development of efficient water-splitting photocatalysts from a dynamic perspective.

New Pathway for Hot Electron Relaxation in Two-Dimensional Heterostructures.

Two-dimensional (2D) heterostructures composed of transition-metal dichalcogenide atomic layers are the new frontier for novel optoelectronic and photovoltaic device applications. Some key properties that make these materials appealing, yet are not well understood, are ultrafast hole/electron dynamics, interlayer energy transfer and the formation of interlayer hot excitons. Here, we study photoexcited electron/hole dynamics in a representative heterostructure, the MoS2/WSe2 interface, which exhibits type II band alignment. Employing time-dependent density functional theory in the time domain, we observe ultrafast charge dynamics with lifetimes of tens to hundreds of femtoseconds. Most importantly, we report the discovery of an interfacial pathway in 2D heterostructures for the relaxation of photoexcited hot electrons through interlayer hopping, which is significantly faster than intralayer relaxation. This finding is of particular importance for understanding many experimentally observed photoinduced processes, including charge and energy transfer at an ultrafast time scale (<1 ps).

Anomalous Dependence of Photocarrier Recombination Time on the Polaron Density of TiO2(110).

Polarons play a crucial role in energy conversion, but the microscopic mechanism remains unclear since they are susceptible to local atomic structures. Here, by employing ab initio nonadiabatic dynamic simulations, we investigate electron-hole (e-h) nonradiative recombination at the rutile TiO2(110) surface with varied amounts of oxygen vacancies (Vo). The isolated Vo facilitates e-h recombination through forming polarons compared to that in the defect-free surface. However, aggregated Vo forming clusters induce an order-of-magnitude acceleration of polaron diffusion by enhancing phonon excitations, which blocks the defect-mediated recombination and thus prolongs the photocarrier lifetime. We find that photoelectrons are driven to migrate toward the top surface due to polaron formation. Our results show the many-body effects of defects and polaron effects on determining the overall recombination rate, which has been ignored in the Shockley-Read-Hall model. The findings explain the controversial experimental observations and suggest that engineering Vo aggregation would instead improve photocatalysis efficiencies in polaronic materials.

Manipulating Weyl quasiparticles by orbital-selective photoexcitation in WTe2.

Optical control of structural and electronic properties of Weyl semimetals allows development of switchable and dissipationless topological devices at the ultrafast scale. An unexpected orbital-selective photoexcitation in type-II Weyl material WTe2 is reported under linearly polarized light (LPL), inducing striking transitions among several topologically-distinct phases mediated by effective electron-phonon couplings. The symmetry features of atomic orbitals comprising the Weyl bands result in asymmetric electronic transitions near the Weyl points, and in turn a switchable interlayer shear motion with respect to linear light polarization, when a near-infrared laser pulse is applied. Consequently, not only annihilation of Weyl quasiparticle pairs, but also increasing separation of Weyl points can be achieved, complementing existing experimental observations. In this work, we provide a new perspective on manipulating the Weyl node singularity and coherent control of electron and lattice quantum dynamics simultaneously.