Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions DOI
Thomas Sayer, Andrés Montoya−Castillo

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(1)

Published: July 1, 2024

Multitime quantum correlation functions are central objects in physical science, offering a direct link between the experimental observables and dynamics of an underlying model. While experiments such as 2D spectroscopy control can now measure quantities, accurate simulation responses remains computationally expensive sometimes impossible, depending on system’s complexity. A natural tool to employ is generalized master equation (GQME), which offer computational savings by extending reference at comparatively trivial cost. However, dynamical methods that tackle chemical systems with atomistic resolution, those semiclassical hierarchy, often suffer from poor accuracy, limiting credence one might lend their results. By combining work accuracy-boosting formulation memory kernels recent multitime GQME, here we show for first time exploit GQME dramatically improve both accuracy coarse mean-field Ehrenfest obtain orders magnitude efficiency gains.

Language: Английский

Coherence in Chemistry: Foundations and Frontiers DOI
Jonathan D. Schultz, Jonathon L. Yuly, Eric A. Arsenault

et al.

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

Citations

9
Simulating Chemistry on Bosonic Quantum Devices DOI
Rishab Dutta,

Delmar G. A. Cabral,

Ningyi Lyu

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(15), P. 6426 - 6441

Published: July 28, 2024

Bosonic quantum devices offer a novel approach to realize computations, where the two-level system (

Language: Английский

Citations

4
Space-local memory in generalized master equations: Reaching the thermodynamic limit for the cost of a small lattice simulation DOI
Srijan Bhattacharyya, Thomas Sayer, Andrés Montoya−Castillo

et al.

The Journal of Chemical Physics, Journal Year: 2025, Volume and Issue: 162(9)

Published: March 5, 2025

The exact quantum dynamics of lattice models can be computationally intensive, especially when aiming for large system sizes and extended simulation times necessary to converge transport coefficients. By leveraging finite memory access long-time using only short-time data, generalized master equations offer a route simulating the problems efficiently. However, such simulations are limited small lattices whose exhibit finite-size artifacts that contaminate coefficient predictions. To address this problem, we introduce novel approach exploits in both time space efficiently predict many-body dissipative involving short-range interactions. This advance enables one leverage nonperturbatively exactly simulate arbitrarily systems over long times. We demonstrate strengths method by focusing on nonequilibrium polaron relaxation dispersive Holstein model, successfully two dimensions free from effects, thereby reducing computational expense multiple orders magnitude. Our is broadly applicable provides an accurate efficient means investigate with microscopic resolution mesoscopic length scales relevant experiments.

Language: Английский

Citations

0
Discrete Generalized Quantum Master Equations DOI

Nancy Makri

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: May 6, 2025

Several derivative and integral approximations are explored for discretizing the Nakajima-Zwanzig generalized quantum master equation (NZ-QME or GQME) to obtain discrete (DQME) hierarchies relations between memory kernel reduced density matrix (RDM) elements. It is shown that simplest forward-difference approximation does not allow reliable determination of elements, even in infinitesimal time-step limit, kernels obtained earlier work flawed, although procedure can be remedied. The various give rise DQMEs differ structure RDM-kernel relationships. use a more accurate discretization based on midpoint leads DQME exhibits endpoint effects, which reflect weaker impact bath RDM during first time step parallel those encountered small decomposition path (SMatPI) with symmetric factorization short-time propagator. features illustrated through analytical examples involving simple integrodifferential scalar GQME model, as well numerical results two-level system (TLS) coupled harmonic bath.

Language: Английский

Citations

0
Nonequilibrium relaxation exponentially delays the onset of quantum diffusion DOI Creative Commons
Srijan Bhattacharyya, Thomas Sayer, Andrés Montoya−Castillo

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2025, Volume and Issue: 122(19)

Published: May 9, 2025

Predicting the exact many-body quantum dynamics of polarons in materials with strong carrier–phonon interactions presents a fundamental challenge, often necessitating one to adopt approximations that sacrifice ability predict transition from nonequilibrium relaxation thermodynamic equilibrium. Here, we exploit recent breakthrough generalizes concept memory beyond its conventional temporal meaning also encompass space. Specifically, leverage our finding observables systems local couplings satisfy Green’s functions kernels are time and This enables us employ small lattices over short times thermodynamically large arbitrarily long timescales while circumventing deleterious impacts finite-size effects. We thus interrogate formation migration one- (1D) two-dimensional (2D) systems, revealing their motion approaches diffusive transport only asymptotically system size. compare 1D 2D investigate effect dimension polaron physics, illustrating how energy variations can cause localization—a phenomenon observable via current microscopy experiments.

Language: Английский

Citations

0
Coarse-Grained Approach to Simulate Signatures of Excitation Energy Transfer in Two-Dimensional Electronic Spectroscopy of Large Molecular Systems DOI Creative Commons
Kai Zhong, Hoàng Long Nguyễn, Thanh Nhut

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(14), P. 6111 - 6124

Published: July 12, 2024

Two-dimensional electronic spectroscopy (2DES) has proven to be a highly effective technique in studying the properties of excited states and process excitation energy transfer complex molecular assemblies, particularly biological light-harvesting systems. However, accurate simulation 2DES for large systems still poses challenge because heavy computational demands it entails. In an effort overcome this limitation, we devised coarse-grained method. This method encompasses treatment entire system by dividing into distinct weakly coupled segments, which are assumed communicate predominantly through incoherent exciton transfer. We first demonstrate efficiency on model dimer system, demonstrates marked improvement calculation efficiency, with results that exhibit good concordance reference spectra calculated less approximate methods. Additionally, application antenna 2 (LH2) purple bacteria showcases its advantages, accuracy, limitations. Furthermore, simulating anisotropy decay LH2 induced comparison experiments confirm is capable accurately describing dynamical processes biologically relevant system. presented lends itself extension accounts effect intrasegment relaxation spectra, ignored implementation reported here. It envisioned will employed future efficiently calculate 2D more extensive systems, such as photosynthetic supercomplexes.

Language: Английский

Citations

3
Combining the generalized quantum master equation approach with quasiclassical mapping Hamiltonian methods to simulate the dynamics of electronic coherences DOI
Yudan Liu, Ellen Mulvihill, Eitan Geva

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(16)

Published: Oct. 22, 2024

The generalized quantum master equation (GQME) approach provides a powerful general-purpose framework for simulating the inherently mechanical dynamics of subset electronic reduced density matrix elements interest in complex molecular systems. Previous studies have found that combining GQME with quasiclassical mapping Hamiltonian (QC/MH) methods can dramatically improve accuracy populations obtained via those methods. In this paper, we perform complimentary study advantages offered by coherences, which play central role optical spectroscopy, information science, and technology. To end, focus on cases where coherences predicted spin-boson benchmark model direct application various QC/MH are inaccurate. We find similar to case populations, also provide comprehensive analysis how performance GQMEs depends choice projection operator basis show feasibility benefit from casting terms eigen-basis observable interest.

Language: Английский

Citations

2
Simulating Non-Markovian Dynamics in Multidimensional Electronic Spectroscopy via Quantum Algorithm DOI
Federico Gallina, Matteo Bruschi, Roberto Cacciari

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 25, 2024

Including the effect of molecular environment in numerical modeling time-resolved electronic spectroscopy remains an important challenge computational spectroscopy. In this contribution, we present a general approach for simulation optical response multichromophore systems structured and its implementation as quantum algorithm. A key step procedure is pseudomode embedding system-environment problem resulting finite set states evolving according to Markovian master equation. This formulation then solved by collision model integrated into algorithm designed simulate linear nonlinear functions. The workflow validated simulating spectra prototypical excitonic dimer interacting with fast (memoryless) finite-memory environments. results demonstrate, on one hand, potential dynamical features spectroscopy, including lineshape, spectral diffusion, relaxations along delay times. On other explicit synthesis circuits provides fully protocol harnessing efficient many-body dynamics promised future generation fault-tolerant computers.

Language: Английский

Citations

2
Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions DOI
Thomas Sayer, Andrés Montoya−Castillo

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(1)

Published: July 1, 2024

Multitime quantum correlation functions are central objects in physical science, offering a direct link between the experimental observables and dynamics of an underlying model. While experiments such as 2D spectroscopy control can now measure quantities, accurate simulation responses remains computationally expensive sometimes impossible, depending on system’s complexity. A natural tool to employ is generalized master equation (GQME), which offer computational savings by extending reference at comparatively trivial cost. However, dynamical methods that tackle chemical systems with atomistic resolution, those semiclassical hierarchy, often suffer from poor accuracy, limiting credence one might lend their results. By combining work accuracy-boosting formulation memory kernels recent multitime GQME, here we show for first time exploit GQME dramatically improve both accuracy coarse mean-field Ehrenfest obtain orders magnitude efficiency gains.

Language: Английский

Citations

1