Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules

Fernández-Alberti, Sebastián; Roitberg, Adrián E.; Nelson, Tammie; Tretiak, Sergei

doi:10.1063/1.4732536

Cited by 201 publications

(319 citation statements)

References 79 publications

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“…Tretiak's group has also developed an algorithm to deal with trivial crossings. 99 Their methodology keeps track of the overlap between electronic states in consecutive time steps (the same overlap functions JK S mentioned above). If the overlap exceeds a certain threshold, the crossing is considered trivial, and the hop takes place with unity probability.…”

Section: Dynamics Near Intersectionsmentioning

confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.

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Section: Dynamics Near Intersectionsmentioning

confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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“…We make use of our previously developed non-adiabatic excited state molecular dynamics (NA-ESMD) framework and implement our recently developed state reassignment algorithm 35 to correctly treat trivial unavoided crossings between the numerous coupled electronic states within the surface hopping methodology. Both the through-bond two-ring→three-ring→four-ring transfer pathway and the through-space direct two-ring→four-ring transfer pathway are investigated.…”

Section: Introductionmentioning

confidence: 99%

Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers

Fernández-Alberti

Roitberg²,

Kleiman³

et al. 2012

The Journal of Chemical Physics

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Non-adiabatic excited-state molecular dynamics is used to study the ultrafast intramolecular energy transfer between two-, three-, and four-ring linear polyphenylene ethynylene chromophore units linked through meta-substitutions. Twenty excited-state electronic energies, with their corresponding gradients and nonadiabatic coupling vectors were included in the simulations. The initial laser excitation creates an exciton delocalized between the different absorbing two-ring linear PPE units. Thereafter, we observe an ultrafast directional change in the spatial localization of the transient electronic transition density. The analysis of the intramolecular flux of the transition density shows a sequential through-bond two-ring→three-ring→four-ring transfer as well as an effective through-space direct two-to-four ring transfer. The vibrational excitations of C≡C stretching motions change according to that. Finally, a mechanism of unidirectional energy transfer is presented based on the variation of the energy gaps between consecutive electronic excited states in response to the intramolecular flux of the transition density. The mechanism resembles a Shishiodoshi Japanese bamboo water fountain where, once the electronic population has been transferred to the state directly below in energy, the two states decouple thereby preventing energy transfer in the opposite direction.

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“…[37][38][39][40][41][42] Further details of the NA-ESMD 5 approach, implementation, and limitations can be found in our previous work. 40,[43][44][45][46][47] Simulation Details and Absorbance Spectra…”

Section: Computation Of Excited States and Na-esmd Methodologymentioning

confidence: 99%

Photoexcited Energy Transfer in a Weakly Coupled Dimer

et al. 2015

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Nonadiabatic excited-state molecular dynamics (NA-ESMD) simulations have been performed in order to study the time-dependent exciton localization during energy transfer between two chromophore units of the weakly coupled anthracene dimer dithia-anthracenophane (DTA). Simulations are done at both low temperature (10 K) and room temperature (300 K). The initial photoexcitation creates an exciton which is primarily localized on a single monomer unit. Subsequently, the exciton experiences an ultrafast energy transfer becoming localized on either one monomer unit or the other, whereas delocalization between both monomers never occurs. In half of the trajectories, the electronic transition density becomes completely localized on the same monomer as the initial excitation, while in the other half, it becomes completely localized on the opposite monomer. In this article, we present an analysis of the energy transfer dynamics and the effect of thermally induced geometry distortions on the exciton localization. Finally, simulated fluorescence anisotropy decay curves for both DTA and the monomer unit dimethyl anthracene (DMA) are compared. Our analysis reveals that changes in the transition density localization caused by energy transfer between two monomers in DTA is not the only source of depolarization and exciton relaxation within a single DTA monomer unit can also cause reorientation of the transition dipole.

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Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules

Cited by 201 publications

References 79 publications

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers

Photoexcited Energy Transfer in a Weakly Coupled Dimer

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