Intermolecular conical intersections in molecular aggregates

Sio, Antonietta De; Sommer, Ephraim; Nguyen, Xuan Trung; Groß, Lynn; Popović, Duško; Nebgen, Benjamin; Fernández-Alberti, Sebastián; Pittalis, Stefano; Rozzi, Carlo Andrea; Molinari, Elisa; Mena‐Osteritz, Elena; Bäuerle, Peter; Frauenheim, Thomas; Tretiak, Sergei; Lienau, Christoph

doi:10.1038/s41565-020-00791-2

Cited by 29 publications

(21 citation statements)

References 59 publications

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“…Simulating the dynamics of processes involving electronically excited molecules requires potential energy surfaces, their gradients, the electronic matrix elements controlling their coupling, and a nonadiabatic dynamics algorithm. − Recent advances on these topics have enabled quantitative accurate simulations for medium-size molecules and qualitatively accurate simulations for nanosized molecules or clusters. − The electronic structure must be treated quantum mechanically, and for simulating all but the smallest systems, one uses a semiclassical treatment of nuclear motion. The present article is concerned with direct dynamics, where, instead of requiring parametrized analytic functions for the energies and couplings, all required energies, forces, and couplings for each geometry that is important for evaluating dynamical properties are obtained directly from electronic structure calculations when they are needed in the dynamics calculation.…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping

Shu

Zhang

Chen

et al. 2022

J. Chem. Theory Comput.

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Direct dynamics by mixed quantum-classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic structure theory. For example, at every time step of a trajectory, nonadiabatic dynamics requires potential energy surfaces, their gradients, and the matrix elements coupling the surfaces. The need for the couplings can be alleviated by employing the time derivatives of the wave functions, which can be evaluated from overlaps of electronic wave functions at successive time steps. However, evaluation of overlap integrals is still expensive for large systems. In addition, for electronic structure methods for which the wave functions or the coupling matrix elements are not available, nonadiabatic dynamics algorithms become inapplicable. In this work, building on recent work by Baeck and An, we propose new nonadiabatic dynamics algorithms that only require adiabatic potential energies and their gradients. The new methods are named curvature-driven coherent switching with decay of mixing (κCSDM) and curvature-driven trajectory surface hopping (κ TSH). We show how powerful these new methods are in terms of computation time and accuracy as compared to previous mixed quantum-classical nonadiabatic dynamics algorithms. The lowering of the computational cost will allow longer nonadiabatic trajectories and greater ensemble averaging to be affordable, and the ability to calculate the dynamics without electronic structure coupling matrix elements extends the dynamics capability to new classes of electronic structure methods.

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Section: Introductionmentioning

confidence: 99%

Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping

Shu

Zhang

Chen

et al. 2022

J. Chem. Theory Comput.

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“…Fourier transform along τ provides, at each T, an absorptive two-dimensional electronic spectrum A 2D (E X , T, E D ) as a function of excitation (E X ) and detection (E D ) energy. 36,50 Details can be found in the Methods section.…”

Section: Resultsmentioning

confidence: 99%

“…Alternatively, physical means, specifically the coupling of molecular excitons to localized electromagnetic field fluctuations, e . g ., in microcavities or localized plasmons at the surface of metallic nanoparticles, may enhance exciton coherence lengths and energy transport properties in molecular aggregates. − An elegant and powerful tool to investigate those phenomena is two-dimensional electronic spectroscopy (2DES), , since it can naturally delineate homogeneous and inhomogeneous line broadening effects. − …”

mentioning

confidence: 99%

Plasmon-Enhanced Exciton Delocalization in Squaraine-Type Molecular Aggregates

et al. 2022

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Enlarging exciton coherence lengths in molecular aggregates is critical for enhancing the collective optical and transport properties of molecular thin film nanostructures or devices. We demonstrate that the exciton coherence length of squaraine aggregates can be increased from 10 to 24 molecular units at room temperature when preparing the aggregated thin film on a metallic rather than a dielectric substrate. Twodimensional electronic spectroscopy measurements reveal a much lower degree of inhomogeneous line broadening for aggregates on a gold film, pointing to a reduced disorder. The result is corroborated by simulations based on a Frenkel exciton model including exciton−plasmon coupling effects. The simulation shows that localized, energetically nearly resonant excitons on spatially well separated segments can be radiatively coupled via delocalized surface plasmon polariton modes at a planar molecule−gold interface. Such plasmon-enhanced delocalization of the exciton wave function is of high importance for improving the coherent transport properties of molecular aggregates on the nanoscale. Additionally, it may help tailor the collective optical response of organic materials for quantum optical applications.

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“…1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 Recent advances on these topics have enabled quantitative accurate simulations for medium-size molecules and qualitatively accurate simulations for nano-sized molecules or clusters. 20,21,22,23,24,25,26,27,28,29,30,31 The electronic structure must be treated quantum mechanically, and for simulating all but the smallest systems, one uses a semiclassical treatment of nuclear motion. The present article is concerned with direct dynamics, where, instead of requiring parametrized analytic functions for the energies and couplings, all required energies, forces, and couplings for each geometry that is important for evaluating dynamical properties are obtained directly from electronic structure calculations when they are needed in the dynamics calculation.…”

Section: Introductionmentioning

confidence: 99%

“…evaluated when the trajectory is terminated. The ensemble-averaged populations in the ground and excited states are shown as functions of time in Fig 1.Alternatively, we can define the population of a certain state I as,(30) where 𝑁 "#$% ! is the number of trajectories for which the pointer state is I when the trajectory is terminated.…”

mentioning

confidence: 99%

Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping

Shu

Zhang

Sun

et al. 2021

Preprint

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Direct dynamics by mixed quantum–classical nonadiabatic methods is an important tool for understanding processes involving multiple electronic states. Very often, the computational bottleneck of such direct simulation comes from electronic structure theory. For example, at every time step of a trajectory, nonadiabatic dynamics requires potential energy surfaces, their gradients, and the matrix elements coupling the surfaces. The need for the couplings can be alleviated by employing the time derivatives of the wave functions, which can be evaluated from overlaps of electronic wave functions at successive timesteps. However, evaluation of overlap integrals is still expensive for large systems. In addition, for electronic structure methods for which the wave functions or the coupling matrix elements are not available, nonadiabatic dynamics algorithms become inapplicable. In this work, building on recent work by Baeck and An, we propose new nonadiabatic dynamics algorithms that only require adiabatic potential energies and their gradients. The new methods are named curvature- driven coherent switching with decay of mixing (κCSDM) and curvature-driven trajectory surface hopping (κTSH). We show how powerful these new methods are in terms of computer time and good agreement with methods employing nonadiabatic coupling vectors computed in conventional ways. The lowering of the computational cost will allow longer nonadiabatic trajectories and greater ensemble averaging to be affordable, and the ability to calculate the dynamics without electronic structure coupling matrix elements extends the dynamics capability to new classes of electronic structure methods.

show abstract

Intermolecular conical intersections in molecular aggregates

Cited by 29 publications

References 59 publications

Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping

Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping

Plasmon-Enhanced Exciton Delocalization in Squaraine-Type Molecular Aggregates

Nonadiabatic Dynamics Algorithms with Only Potential Energies and Gradients: Curvature-Driven Coherent Switching with Decay of Mixing and Curvature-Driven Trajectory Surface Hopping

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