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1. Ultrafast many-body bright–dark exciton transition in anatase TiO ₂

   https://doi.org/10.1073/pnas.2307671120  

   Wang, Aolei; Jiang, Xiang; Zheng, Qijing; Petek, Hrvoje; Zhao, Jin (November 2023, Proceedings of the National Academy of Sciences)

   The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose–Einstein condensation, and light-energy harvesting. Anatase TiO₂with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe–Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO₂. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron–phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron–hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright–dark exciton transitions sheds insights into applications of anatase TiO₂in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors. 

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2. Ab initio calculations of spin-nonconserving exciton–phonon scattering in monolayer transition metal dichalcogenides

   https://doi.org/10.1088/1361-648X/ac6649  

   Zhang, Xiao-Wei; Cao, Ting (April 2022, Journal of Physics: Condensed Matter)

   Abstract We investigate the spin-nonconserving relaxation channel of excitons by their couplings with phonons in two-dimensional transition metal dichalcogenides using ab initio approaches. Combining GW-Bethe–Salpeter equation method and density functional perturbation theory, we calculate the electron–phonon and exciton–phonon coupling matrix elements for the spin-flip scattering in monolayer WSe 2 , and further analyze the microscopic mechanisms influencing these scattering strengths. We find that phonons could produce effective in-plane magnetic fields which flip spin of excitons, giving rise to relaxation channels complimentary to the spin-conserving relaxation. Finally, we calculate temperature-dependent spin-flip exciton–phonon relaxation times. Our method and analysis can be generalized to study other two-dimensional materials and would stimulate experimental measurements of spin-flip exciton relaxation dynamics. 

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3. Exciton dispersion and exciton–phonon interaction in solids by time-dependent density functional theory

   https://doi.org/10.1063/5.0137326  

   Liu, Junyi; Lu, Gang; Zhang, Xu (January 2023, The Journal of Chemical Physics)

   Understanding, predicting, and ultimately controlling exciton band structure and exciton dynamics are central to diverse chemical and materials problems. Here, we have developed a first-principles method to determine exciton dispersion and exciton–phonon interaction in semiconducting and insulating solids based on time-dependent density functional theory. The first-principles method is formulated in planewave bases and pseudopotentials and can be used to compute exciton band structures, exciton charge density, ionic forces, the non-adiabatic coupling matrix between excitonic states, and the exciton–phonon coupling matrix. Based on the spinor formulation, the method enables self-consistent noncollinear calculations to capture spin-orbital coupling. Hybrid exchange-correlation functionals are incorporated to deal with long-range electron–hole interactions in solids. A sub-Hilbert space approximation is introduced to reduce the computational cost without loss of accuracy. For validations, we have applied the method to compute the exciton band structure and exciton–phonon coupling strength in transition metal dichalcogenide monolayers; both agree very well with the previous GW-Bethe–Salpeter equation and experimental results. This development paves the way for accurate determinations of exciton dynamics in a wide range of solid-state materials. 

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4. Parametric dependence of hot electron relaxation timescales on electron-electron and electron-phonon interaction strengths

   https://doi.org/10.1038/s42005-020-00442-x  

   Wilson, Richard B.; Coh, Sinisa (December 2020, Communications Physics)

   null (Ed.)

   Abstract Understanding how photoexcited electron dynamics depend on electron-electron (e-e) and electron-phonon (e-p) interaction strengths is important for many fields, e.g. ultrafast magnetism, photocatalysis, plasmonics, and others. Here, we report simple expressions that capture the interplay of e-e and e-p interactions on electron distribution relaxation times. We observe a dependence of the dynamics on e-e and e-p interaction strengths that is universal to most metals and is also counterintuitive. While only e-p interactions reduce the total energy stored by excited electrons, the time for energy to leave the electronic subsystem also depends on e-e interaction strengths because e-e interactions increase the number of electrons emitting phonons. The effect of e-e interactions on energy-relaxation is largest in metals with strong e-p interactions. Finally, the time high energy electron states remain occupied depends only on the strength of e-e interactions, even if e-p scattering rates are much greater than e-e scattering rates. 

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5. Modeling Spin-Crossover Dynamics

   https://doi.org/10.1146/annurev-physchem-101419-012625  

   Mukherjee, Saikat; Fedorov, Dmitry A.; Varganov, Sergey A. (April 2021, Annual Review of Physical Chemistry)

   In this article, we review nonadiabatic molecular dynamics (NAMD) methods for modeling spin-crossover transitions. First, we discuss different representations of electronic states employed in the grid-based and direct NAMD simulations. The nature of interstate couplings in different representations is highlighted, with the main focus on nonadiabatic and spin-orbit couplings. Second, we describe three NAMD methods that have been used to simulate spin-crossover dynamics, including trajectory surface hopping, ab initio multiple spawning, and multiconfiguration time-dependent Hartree. Some aspects of employing different electronic structure methods to obtain information about potential energy surfaces and interstate couplings for NAMD simulations are also discussed. Third, representative applications of NAMD to spin crossovers in molecular systems of different sizes and complexities are highlighted. Finally, we pose several fundamental questions related to spin-dependent processes. These questions should be possible to address with future methodological developments in NAMD. 

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