Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach

Fernández-Alberti, Sebastián; Makhov, Dmitry V.; Tretiak, Sergei; Shalashilin, Dmitrii V.

doi:10.1039/c5cp07332d

Cited by 60 publications

(106 citation statements)

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“…46,[255][256][257][258] Certain nonadiabatic molecular dynamics methods can miss those localized regions for numerical reasons, and one way to monitor the presence of TUCs is by looking for abrupt changes in the electronic wavefunction of the running state -via wavefunction overlap at different time stepstesting for a rapid change of the corresponding electronic character. 127,[259][260] Based on those considerations and the development of a norm-preserving interpolation strategy for the calculation of time-derivative couplings, 261 AIMS was adapted to efficiently detect and properly describe TUCs. 254 Until now, we have only discussed internal conversion processes, which are nonradiative transitions between electronic states sharing the same spin-multiplicity.…”

Section: Nonadiabatic Dynamicsmentioning

confidence: 99%

Ab Initio Nonadiabatic Quantum Molecular Dynamics

2018

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The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born-Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump-probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third class of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.

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Section: Nonadiabatic Dynamicsmentioning

confidence: 99%

Ab Initio Nonadiabatic Quantum Molecular Dynamics

2018

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“…For example, AIMS has been successfully used to compute and interpret experimental observables, and even predict them years before their actual experimental measurement . The mechanism of photoinduced energy transfer between the building blocks in a phenylene ethynylene dendrimer was identified by using a special variant of AIMCE, employing a time‐dependent diabatic basis . The complex excited‐state dynamics of formamide, comprising eight coupled electronic states, was investigated using DD‐vMCG dynamics.…”

Section: Applications Of Nonadiabatic Molecular Dynamicsmentioning

confidence: 99%

Different flavors of nonadiabatic molecular dynamics

Agostini

Curchod

2019

WIREs Comput Mol Sci

100

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The Born‐Oppenheimer approximation constitutes a cornerstone of our understanding of molecules and their reactivity, partly because it introduces a somewhat simplified representation of the molecular wavefunction. However, when a molecule absorbs light containing enough energy to trigger an electronic transition, the simplistic nature of the molecular wavefunction offered by the Born‐Oppenheimer approximation breaks down as a result of the now non‐negligible coupling between nuclear and electronic motion, often coined nonadiabatic couplings. Hence, the description of nonadiabatic processes implies a change in our representation of the molecular wavefunction, leading eventually to the design of new theoretical tools to describe the fate of an electronically‐excited molecule. This Overview focuses on this quantity—the total molecular wavefunction—and the different approaches proposed to describe theoretically this complicated object in non‐Born‐Oppenheimer conditions, namely the Born‐Huang and Exact‐Factorization representations. The way each representation depicts the appearance of nonadiabatic effects is then revealed by using a model of a coupled proton–electron transfer reaction. Applying approximations to the formally exact equations of motion obtained within each representation leads to the derivation, or proposition, of different strategies to simulate the nonadiabatic dynamics of molecules. Approaches like quantum dynamics with fixed and time‐dependent grids, traveling basis functions, or mixed quantum/classical like surface hopping, Ehrenfest dynamics, or coupled‐trajectory schemes are described in this Overview. This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics Software > Simulation Methods Theoretical and Physical Chemistry > Spectroscopy

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“…The dynamical problem, however, is complex for a full quantum treatment, even assuming one has perfect knowledge on PES and non-adiabatic couplings, due to high dimensionality of the configuration space, even in the closed dynamics case. Even sophisticated computational schemes, capable of performing quantum mechanical simulations [37][38][39], including such clever approaches as spawning [40,41], scale unfavorably with the number of atoms, so that much more cost-efficient semiclassical or/and mixed quantum-classical methods are highly desired.…”

Section: Introductionmentioning

confidence: 99%