Consistent Construction of the Density Matrix from Surface Hopping Trajectories

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(6), С. 2349 - 2361

Опубликована: Март 16, 2024

Proper construction of the density matrix based on surface hopping trajectories remains a difficult problem. Due to well-known overcoherence in traditional simulations, electronic wave function cannot be used directly. In this work, we propose consistent method, which takes advantage occupation active states rescale coherence calculated by functions and ensures intrinsic consistency matrix. This new trajectory analysis method can for both Tully's fewest switches (FSSH) our recently proposed branching corrected (BCSH). As benchmarked one- two-dimensional standard scattering models, approach combined with BCSH achieves highly accurate time-dependent spatial distributions adiabatic populations compared exact quantum results.

Язык: Английский

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Detailed Complementary Consistency: Wave Function Tells Particle How to Hop, Particle Tells Wave Function How to Collapse

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(26), С. 6771 - 6781

Опубликована: Июнь 24, 2024

In mixed quantum-classical dynamics, the quantum subsystem can have both wave function and particle-like descriptions. However, they may yield inconsistent results for expectation value of same physical quantity. We here propose a novel detailed complementary consistency (DCC) method based on principle internal consistency. Namely, along each trajectory tells particle how to hop, while collapse active states in ensemble. As benchmarked diverse array representative models with localized nonadiabatic couplings, DCC not only achieves fully consistent (i.e., identical populations calculated functions states) but also closely reproduces exact results. Due high performance, our new has great potential give accurate description general dynamics after further development.

Язык: Английский

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Pseudo-heterostructure and condensation of 1D moiré excitons in twisted phosphorene bilayers

Science Advances, Год журнала: 2023, Номер 9(29)

Опубликована: Июль 21, 2023

Heterostructures are not expected to form in a single homogeneous material. Here, we show that planar pseudo-heterostructures could emerge twisted bilayer of phosphorene (tbP), driving in-plane energy and charge transfer. The formation moiré superlattices combined with electronic anisotropy tbPs yields one-dimensional (1D) excitons long radiative nonradiative lifetimes, large binding energies, deep potentials. Low-frequency phonons dynamic potentials revealed be responsible for the energy/charge transfer exciton dynamics. 1D predicted exhibit Bose-Einstein condensation at high temperatures may lead exotic Tonks-Girardeau Bose gases.

Язык: Английский

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Nonadiabatic Molecular Dynamics with Subsystem Density Functional Theory: Application to Crystalline Pentacene

Journal of Physics Condensed Matter, Год журнала: 2024, Номер 36(38), С. 385901 - 385901

Опубликована: Июнь 12, 2024

In this work, we report the development and assessment of nonadiabatic molecular dynamics approach with electronic structure calculations based on linearly scaling subsystem density functional method. The is implemented in an open-source embedded Quantum Espresso/Libra software specially designed for simulations extended systems. As proof applicability method to large condensed-matter systems, examine nonradiative relaxation excess excitation energy pentacene crystals simulation supercells containing more than 600 atoms. We find that increased structural disorder observed larger supercell models induces couplings states accelerates excited states. conduct a comparative analysis several quantum-classical trajectory surface hopping schemes, including two new methods proposed work (revised decoherence-induced instantaneous decoherence at frustrated hops). Most tested schemes suggest fast occurring timescales 0.7-2.0 ps range, but they significantly overestimate ground state recovery rates. Only modified simplified decay mixing yields notably slower 8-14 ps, inhibited recovery.

Язык: Английский

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Relaxation of Photoexcited Electron–Hole Pairs at Si(111) Surfaces with Adsorbed Ag Monolayered Clusters of Increasing Size

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 2905 - 2913

Опубликована: Март 11, 2025

The efficiency of silicon solar cells is affected by the light absorption and recombination losses photoexcited charge carries. One possible way to improve through deposition transition metal nanoparticles on Si surfaces. Here, we first carry out density functional theory (DFT) calculations obtain electronic structures for Agn (n = 1–7) monolayered clusters adsorbed Si(111)/H Results are presented in form states, band gaps, absorption, which allow investigation interaction Ag with Si. Different behaviors can be expected depending size deposited clusters. Overall, leads smaller red-shifts, large increases compared pristine slab. We then study relaxation dynamics electron–hole pairs slabs based nonadiabatic couplings using reduced matrix approach within Redfield formalism. Nonradiative rates noticeably different various transitions. observes higher surfaces adsorbates than surface due transfer events involving orbitals. also compute emission spectra from excited-state dynamics. gap dark indirect nature its gap. addition larger breaks symmetry slabs, enabling These thus exhibit bright emission. introduction advantageous applications photovoltaics photocatalysis.

Язык: Английский

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First-principles study of tunable exciton lifetime in ZrSSe/SnSSe heterostructures

Applied Surface Science, Год журнала: 2025, Номер unknown, С. 163221 - 163221

Опубликована: Апрель 1, 2025

Язык: Английский

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Ultrafast Bright-to-Dark Exciton Relaxation in Bilayer Borophene Driven by Strong Excitonic Effects

Nano Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 20, 2025

Exciton dynamics in the recently discovered bilayer borophene (BL-α5, consisting of two stacked v1/12 boron sheets) are great interest due to this material's promising electronic and optical properties for nano-optoelectronic applications. Using a GW plus real-time Bethe-Salpeter equation (GW-rtBSE) approach ab initio nonadiabatic molecular (NAMD), we identify Frenkel-type lowest-energy bright exciton spatially delocalized dark BL-α5, with large binding energies ∼700 ∼502 meV, respectively. The electron-hole (e-h) Coulomb interaction (exciton effect) dominates over electron-phonon (e-ph) scattering, playing pivotal role an ultrafast bright-to-dark transition relaxation time ∼150 fs. Furthermore, excitons undergo nonradiative recombination on picosecond scale (∼14 ps at room temperature). These results provide theoretical foundation potential light-energy harvesting applications borophene.

Язык: Английский

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What is Missing in the Mean Field Description of Spatial Distribution of Population? Important Role of Auxiliary Wave Packets in Trajectory Branching

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(44), С. 9855 - 9863

Опубликована: Окт. 27, 2023

When the traditional Ehrenfest mean field approach is employed to simulate nonadiabatic dynamics, an effective wave packet (WP) on average potential energy surface (PES) utilized describe nuclear motion. In fully quantum picture, however, WP components different adiabatic PESs gradually separate in space because they evolve under velocities and forces. Due trajectory branching of components, proper decoherence needs be taken into account, spatial distribution population cannot described by a single WP. Here, we propose auxiliary corrected (A-BCMF) method, where trajectories WPs are introduced. As benchmarked three standard Tully models, A-BCMF not only gives correct channel populations but also captures accurate time-dependent population. Thereby, reveal important role solving intrinsic problems widely used description dynamics.

Язык: Английский

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Consistent Construction of Density Matrix from Surface Hopping Trajectories

Опубликована: Фев. 9, 2024

Proper construction of density matrix based on surface hopping trajectories remains a difficult problem. Due to the well-known overcoherence in traditional simulations, electronic wavefunction cannot be used directly. In this work, we propose consistent method, which takes advantage occupation active states rescale coherence calculated by wavefunctions and ensures intrinsic consistency matrix. This new trajectory analysis method can for both Tully’s fewest switches (FSSH) our recently proposed branching corrected (BCSH). As benchmarked one- two-dimensional standard scattering models, approach combined with BCSH achieves highly accurate time-dependent spatial distributions adiabatic populations compared exact quantum results.

Язык: Английский

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A Review of Bandgap Engineering and Prediction in 2D Material Heterostructures: A DFT Perspective

International Journal of Molecular Sciences, Год журнала: 2024, Номер 25(23), С. 13104 - 13104

Опубликована: Дек. 6, 2024

The advent of two-dimensional (2D) materials and their capacity to form van der Waals (vdW) heterostructures has revolutionized numerous scientific fields, including electronics, optoelectronics, energy storage. This paper presents a comprehensive investigation bandgap engineering band structure prediction in 2D vdW utilizing density functional theory (DFT). By combining various materials, such as graphene, hexagonal boron nitride (h-BN), transition metal dichalcogenides, blue phosphorus, these exhibit tailored properties that surpass those individual components. Bandgap represents an effective approach addressing the limitations inherent material properties, thereby providing enhanced functionalities for range applications, transistors, photodetectors, solar cells. Furthermore, this study discusses current challenges associated with highlights future prospects aimed at unlocking full potential advanced technological applications.

Язык: Английский

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