Quantum molecular dynamics simulations of the effect of secondary modes on the photoisomerization of a retinal chromophore model

Pereira, Ari; Knapik, Joachim; Chen, Ahai; Lauvergnat, David; Agostini, Federica

doi:10.1140/epjs/s11734-023-00923-4

Cited by 4 publications

(1 citation statement)

References 62 publications

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“…While the coupling of the trajectories adds computational complexity with respect to independent-trajectory methods, an efficient parallelization scheme could mitigate this increased cost. The scaling of these methods with system size is linear and quadratic with the number of trajectories. Note that when interfaced with ab initio quantum chemistry codes, the computational bottleneck is generally the electronic structure calculations rather than the coupled-trajectory dynamics (since the coupling among the trajectories does not require additional electronic structure calculations).…”

Section: Theoretical Backgroundmentioning

confidence: 99%

Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics

Arribas,

Ibele,

Lauvergnat

et al. 2023

J. Chem. Theory Comput.

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Through approximating electron−nuclear correlation terms in the exact factorization approach, trajectory-based methods have been derived and successfully applied to the dynamics of a variety of light-induced molecular processes, capturing quantum (de)coherence effects rigorously. These terms account for the coupling among the trajectories, recovering the nonlocal nature of quantum nuclear dynamics that is completely overlooked in traditional independent-trajectory algorithms. Nevertheless, some of the approximations introduced in the derivation of some of these methods do not conserve the total energy. We analyze energy conservation in the coupledtrajectory mixed quantum-classical (CTMQC) algorithm and explore the performance of a modified algorithm, CTMQC-E, where some of the terms are redefined to restore energy conservation. A set of molecular models is used as a test, namely, 2-cis-penta-2,4-dienimium cation, bis(methylene) adamantyl radical cation, butatriene cation, uracil radical cation, and neutral pyrazine.

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Section: Theoretical Backgroundmentioning

confidence: 99%

Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics

Arribas,

Ibele,

Lauvergnat

et al. 2023

J. Chem. Theory Comput.

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Nonadiabatic dynamics with classical trajectories: The problem of an initial coherent superposition of electronic states

Villaseco Arribas,

Maitra,

Agostini

2024

The Journal of Chemical Physics

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Advances in coherent light sources and development of pump–probe techniques in recent decades have opened the way to study electronic motion in its natural time scale. When an ultrashort laser pulse interacts with a molecular target, a coherent superposition of electronic states is created and the triggered electron dynamics is coupled to the nuclear motion. A natural and computationally efficient choice to simulate this correlated dynamics is a trajectory-based method where the quantum-mechanical electronic evolution is coupled to a classical-like nuclear dynamics. These methods must approximate the initial correlated electron–nuclear state by associating an initial electronic wavefunction to each classical trajectory in the ensemble. Different possibilities exist that reproduce the initial populations of the exact molecular wavefunction when represented in a basis. We show that different choices yield different dynamics and explore the effect of this choice in Ehrenfest, surface hopping, and exact-factorization-based coupled-trajectory schemes in a one-dimensional two-electronic-state model system that can be solved numerically exactly. This work aims to clarify the problems that standard trajectory-based techniques might have when a coherent superposition of electronic states is created to initialize the dynamics, to discuss what properties and observables are affected by different choices of electronic initial conditions and to point out the importance of quantum-momentum-induced electronic transitions in coupled-trajectory schemes.

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Managing temperature in open quantum systems strongly coupled with structured environments

Le Dé,

Jaouadi,

Mangaud

et al. 2024

The Journal of Chemical Physics

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In non-perturbative non-Markovian open quantum systems, reaching either low temperatures with the hierarchical equations of motion (HEOM) or high temperatures with the Thermalized Time Evolving Density Operator with Orthogonal Polynomials Algorithm (T-TEDOPA) formalism in Hilbert space remains challenging. We compare different ways of modeling the environment. Sampling the Fourier transform of the bath correlation function, also called temperature dependent spectral density, proves to be very effective. T-TEDOPA [Tamascelli et al., Phys. Rev. Lett. 123, 090402 (2019)] uses a linear chain of oscillators with positive and negative frequencies, while HEOM is based on the complex poles of an optimized rational decomposition of the temperature dependent spectral density [Xu et al., Phys. Rev. Lett. 129, 230601 (2022)]. Resorting to the poles of the temperature independent spectral density and of the Bose function separately is an alternative when the problem due to the huge number of Bose poles at low temperatures is circumvented. Two examples illustrate the effectiveness of the HEOM and T-TEDOPA approaches: a benchmark pure dephasing case and a two-bath model simulating the dynamics of excited electronic states coupled through a conical intersection. We show the efficiency of T-TEDOPA to simulate dynamics at a finite temperature by using either continuous spectral densities or only all the intramolecular oscillators of a linear vibronic model calibrated from ab initio data of a phenylene ethynylene dimer.

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Quantum molecular dynamics simulations of the effect of secondary modes on the photoisomerization of a retinal chromophore model

Cited by 4 publications

References 62 publications

Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics

Significance of Energy Conservation in Coupled-Trajectory Approaches to Nonadiabatic Dynamics

Nonadiabatic dynamics with classical trajectories: The problem of an initial coherent superposition of electronic states

Managing temperature in open quantum systems strongly coupled with structured environments

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