Carriers, Quasi-particles, and Collective Excitations in Halide Perovskites

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(13), P. 8154 - 8231

Published: June 5, 2023

Halide perovskites (HPs) are potential game-changing materials for a broad spectrum of optoelectronic applications ranging from photovoltaics, light-emitting devices, lasers to radiation detectors, ferroelectrics, thermoelectrics, etc. Underpinning this spectacular expansion is their fascinating photophysics involving complex interplay carrier, lattice, and quasi-particle interactions spanning several temporal orders that give rise remarkable optical electronic properties. Herein, we critically examine distill dynamical behavior, collective interactions, underlying mechanisms in conjunction with the experimental approaches. This review aims provide unified photophysical picture fundamental understanding outstanding light-harvesting properties HPs. The hotbed carrier uncovered HPs underscores critical role ultrafast spectroscopy studies advancing perovskite optoelectronics.

Language: Английский

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From a one-mode to a multi-mode understanding of conical intersection mediated ultrafast organic photochemical reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(8), P. 2643 - 2687

Published: Jan. 1, 2023

Over the last few decades, conical intersections (CoIns) have grown from theoretical curiosities into common mechanistic features of photochemical reactions, whose function is to funnel electronically excited molecules back their ground state in regions where potential energy surfaces (PESs) two electronic states become degenerate. Analogous transition thermal chemistry, CoIns appear as transient structures providing a kinetic bottleneck along reaction coordinate. However, such not associated with probability crossing an barrier but rather decay full "line" connected by non-reactive modes, intersection space (IS). This article will review our understanding factors controlling CoIn mediated ultrafast taking physical organic chemist approach discussing number case studies for small and photoactive proteins. Such discussion be carried out first introducing "standard" one-mode model based on Landau-Zener (LZ) theory describe reactive event intercepting, locally, single direction, then modern perspective effects phase matching multiple modes same local event, thus redefining expanding description The direct proportionality between slope (or velocity) one mode at widely applied fundamental principle that follows LZ model, yet it fails provide complete reactions coordinate changes IS. We show these situations, particular focussing rhodopsin double bond photoisomerization, mandatory consider additional molecular relationship approaching IS, hence key photochemistry those modes. anticipate this qualitative should considered rational design any process, impacting various fields research ranging photobiology light-driven devices.

Language: Английский

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Plasmon mediated coherent population oscillations in molecular aggregates

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Dec. 5, 2023

Language: Английский

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Reference Energies for Double Excitations: Improvement and Extension

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(13), P. 5655 - 5678

Published: June 17, 2024

In the realm of photochemistry, significance double excitations (also known as doubly excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement key electronic transitions essential light-induced chemical reactions well challenging nature from computational theoretical chemistry point view. Based on state-of-the-art structure methods (such high-order coupled-cluster, selected configuration interaction, and multiconfigurational methods), we improve expand our prior set accurate reference excitation energies for states exhibiting a substantial amount [Loos et al. J. Chem. Theory Comput. 2019, 15, 1939]. This extended collection encompasses 47 across 26 molecular systems that separate into distinct subsets: (i) 28 "genuine" almost exclusively involve configurations (ii) 19 "partial" which exhibit more balanced character between singly configurations. For each subset, assess performance coupled-cluster (CC3, CCSDT, CC4, CCSDTQ) (CASPT2, CASPT3, PC-NEVPT2, SC-NEVPT2). Using probe percentage single involved given transition (%T1) computed at CC3 level, also propose simple correction reduces errors by factor 3, both sets excitations. We hope this complete diverse compilation will help future developments excited-state methodologies.

Language: Английский

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Time-Resolved Dynamics of Metal Halide Perovskite under High Pressure: Recent Progress and Challenges

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(6), P. 1623 - 1635

Published: Feb. 2, 2024

Metal halide perovskites have garnered significant attention in the scientific community for their promising applications optoelectronic devices. The application of pressure engineering, a viable technique, has played crucial role substantially improving characteristics perovskites. Despite notable progress understanding ground-state structural changes under high pressure, comprehensive exploration excited-state dynamics influencing luminescence remains incomplete. This Perspective delves into recent advances time-resolved studies photoexcited metal pressure. With focus on intricate interplay between alterations and electronic properties, we investigate electron–phonon interactions, carrier transport mechanisms, influential roles self-trapped excitons (STEs) coherent phonons luminescence. However, challenges persist, notably need more advanced measurement techniques deeper phenomena induced by

Language: Английский

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Efficient formulation of multitime generalized quantum master equations: Taming the cost of simulating 2D spectra

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(4)

Published: Jan. 25, 2024

Modern 4-wave mixing spectroscopies are expensive to obtain experimentally and computationally. In certain cases, the unfavorable scaling of quantum dynamics problems can be improved using a generalized master equation (GQME) approach. However, inclusion multiple (light–matter) interactions complicates motion leads seemingly unavoidable cubic in time. this paper, we present formulation that greatly simplifies reduces computational cost previous work extended GQME framework treat arbitrary numbers measurements. Specifically, remove time derivatives correlation functions from modified Mori–Nakajima–Zwanzig by switching discrete-convolution implementation inspired transfer tensor We then demonstrate method’s capabilities simulating 2D electronic spectra for excitation-energy-transfer dimer model. our method, resolution data arbitrarily coarsened, especially along t2 axis, which mirrors how obtained experimentally. Even modest case, demands O(103) fewer points. further able decompose into one-, two-, three-time correlations, showing when system enters Markovian regime where measurements unnecessary predict future becomes quadratic. This offers ability generate long-time only short-time data, enabling access timescales previously beyond reach standard methodologies.

Language: Английский

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Coherence in Chemistry: Foundations and Frontiers

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(21), P. 11641 - 11766

Published: Oct. 23, 2024

Coherence refers to correlations in waves. Because matter has a wave-particle nature, it is unsurprising that coherence deep connections with the most contemporary issues chemistry research (e.g., energy harvesting, femtosecond spectroscopy, molecular qubits and more). But what does word "coherence" really mean context of molecules other quantum systems? We provide review key concepts, definitions, methodologies, surrounding phenomena chemistry, we describe how terms "quantum coherence" refer many different chemistry. Moreover, show these notions are related concept an interference pattern. indeed complex, ambiguous definitions may spawn confusion. By describing contexts for sciences, aim enhance understanding communication this broad active area

Language: Английский

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Electronic-vibrational resonance damping time-dependent photosynthetic energy transfer acceleration revealed by 2D electronic spectroscopy

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(5)

Published: Feb. 4, 2025

The effects of damping time electronic-vibrational resonance modes on energy transfer in photosynthetic light-harvesting systems are examined. Using the hierarchical equations motion (HEOM) method, we simulate linear absorption and two-dimensional electronic spectra (2DES) for a dimer model based bottleneck sites complex photosystem II. A site-dependent spectral density is incorporated, with only low-energy site being coupled to mode. Similar patterns observed early 2DES various times, owing weak coupling strength. However, notable differences emerge dynamics high-energy diagonal cross-peaks 2DES. It found that accelerates process, rates increased as extended, but impact becomes negligible when exceeds certain threshold. To evaluate reliability perturbation modified Redfield (MR) method employed under same conditions. results from MR aligned those obtained HEOM predicts faster dynamics.

Language: Английский

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Polariton spectra under the collective coupling regime. II. 2D non-linear spectra

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(7)

Published: Feb. 20, 2025

In our previous work [Mondal et al., J. Chem. Phys. 162, 014114 (2025)], we developed several efficient computational approaches to simulate exciton–polariton dynamics described by the Holstein–Tavis–Cummings (HTC) Hamiltonian under collective coupling regime. Here, incorporated these strategies into previously Lindblad-partially linearized density matrix (L-PLDM) approach for simulating 2D electronic spectroscopy (2DES) of particular, apply quantum propagation scheme in Paper I both forward and backward propagations PLDM develop an importance sampling graphics processing unit vectorization that allow us reduce costs from O(K2)O(T3) O(K)O(T0) 2DES simulation, where K is number states T time steps propagation. We further simulated HTC regime analyzed signal rephasing non-rephasing contributions ground state bleaching, excited emission, stimulated emission pathways.

Language: Английский

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Equation-of-Motion Methods for the Calculation of Femtosecond Time-Resolved 4-Wave-Mixing and N-Wave-Mixing Signals

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17339 - 17396

Published: Oct. 24, 2022

Femtosecond nonlinear spectroscopy is the main tool for time-resolved detection of photophysical and photochemical processes. Since most systems chemical interest are rather complex, theoretical support indispensable extraction intrinsic system dynamics from detected spectroscopic responses. There exist two alternative formalisms calculation signals, response-function (NRF) approach equation-of-motion (EOM) approach. In NRF formalism, system–field interaction assumed to be sufficiently weak treated in lowest-order perturbation theory each laser pulse interacting with sample. The conceptual method signals solutions quantum mechanical, semiclassical, or quasiclassical EOMs which govern time evolution material radiation field pulses. formalism its applications a broad range have been comprehensively reviewed literature. This article provides detailed review suite EOM methods, including 4-wave-mixing N-wave-mixing strong fields. Under certain circumstances, methods may more efficient than computation various signals.

Language: Английский

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