Time-Domain Ab Initio Modeling of Photoinduced Dynamics at Nanoscale Interfaces

Abstract

Nonequilibrium processes involving electronic and vibrational degrees of freedom in nanoscale materials are under active experimental investigation. Corresponding theoretical studies are much scarcer. The review starts with the basics of time-dependent density functional theory, recent developments in nonadiabatic molecular dynamics, and the fusion of the two techniques. Ab initio simulations of this kind allow us to directly mimic a great variety of time-resolved experiments performed with pump-probe laser spectroscopies. The focus is on the ultrafast photoinduced charge and exciton dynamics at interfaces formed by two complementary materials. We consider purely inorganic materials, inorganic-organic hybrids, and all organic interfaces, involving bulk semiconductors, metallic and semiconducting nanoclusters, graphene, carbon nanotubes, fullerenes, polymers, molecular crystals, molecules, and solvent. The detailed atomistic insights available from time-domain ab initio studies provide a unique description and a comprehensive understanding of the competition between electron transfer, thermal relaxation, energy transfer, and charge recombination processes. These advances now make it possible to directly guide the development of organic and hybrid solar cells, as well as photocatalytic, electronic, spintronic, and other devices relying on complex interfacial dynamics.

Ultrafast Electronic Energy Transfer in an Orthogonal Molecular Dyad

“…[21][22][23] For the system in our study, nonadiabatic ab initio molecular dynamics (NA-AIMD) simulations are nowadays feasible. [24][25][26] In our case the description of electronic states and excitations is firmly based on (time-dependent) density functional theory (TDDFT),…”

What Makes the Photocatalytic CO2 Reduction on N-Doped Ta2O5 Efficient: Insights from Nonadiabatic Molecular Dynamics

“…For more details on the NA-MD method and its trajectory surface hopping implementation, we refer the reader to the original works[70][71][72] and related review papers [73][74][75][76][77]. We are interested in the dynamics of population transfer from the donor states localized on N-Ta2 O 5 to the acceptor states of the Ru complexes.…”

Communication: Global flux surface hopping in Liouville space

“…14,15 Despite its great successes, traditional FSSH in Hilbert space has limitations in application to certain phenomena. [15][16][17] Various modifications and corrections have been introduced, a) Electronic addresses: linjun.wang@usc.edu and prezhdo@usc.edu using FSSH as the initial platform. For instance, FSSH has been combined with classical molecular dynamics to build QM/MM-type techniques for large-scale simulations.…”