Quantum dynamics of a vibronically coupled linear chain using a surrogate Hamiltonian approach

Lee, Myeong H.; Troisi, Alessandro

doi:10.1063/1.4953043

Cited by 6 publications

(2 citation statements)

References 101 publications

(128 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The estimate both supports the zero-order framework and indicates quantitative refinements will be needed (especially for multiple resonant vibrations, which can be used to effectively incorporate the first stages of vibronic decoherence and vibrational relaxation into the nonadiabatic dynamics-see Ref. 81).…”

Section: Discussionsupporting

confidence: 60%

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

Tiwari

Jonas

2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.

show abstract

Section: Discussionsupporting

confidence: 60%

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

Tiwari

Jonas

2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…(Description of system-bath interaction is provided in more detail in ref. 46 ) In the local system-bath interaction Hamiltonian transitions involving only one vibrational quantum on the same molecular unit are allowed:…”

Section: Methodsmentioning

confidence: 99%

Vibronic enhancement of excitation energy transport: Interplay between local and non-local exciton-phonon interactions

Lee

Troisi

2017

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

It has been reported in recent years that vibronic resonance between vibrational energy of the intramolecular nuclear mode and excitation-energy difference is crucial to enhance excitation energy transport in light harvesting proteins. Here we investigate how vibronic enhancement induced by vibronic resonance is influenced by the details of local and non-local exciton-phonon interactions. We study a heterodimer model with parameters relevant to the light-harvesting proteins with the surrogate Hamiltonian quantum dynamics method in a vibronic basis. In addition, the impact of field-driven excitation on the efficiency of population transfer is compared with the instantaneous excitation, and the effect of multi-mode vibronic coupling is presented in comparison with the coupling to a single effective vibrational mode. We find that vibronic enhancement of site population transfer is strongly suppressed with the increase of non-local exciton-phonon interaction and increasing the number of strongly coupled high-frequency vibrational modes leads to a further decrease in vibronic enhancement. Our results indicate that vibronic enhancement is present but may be much smaller than previously thought and therefore care needs to be taken when interpreting its role in excitation energy transport. Our results also suggest that non-local exciton-phonon coupling, which is related to the fluctuation of the excitonic coupling, may be as important as local exciton-phonon coupling and should be included in any quantum dynamics model.

show abstract

Polaron stability in oligoacene crystals

Pereira

Ribeiro

2017

J Mol Model

View full text Add to dashboard Cite

The polaron stability in organic molecular crystals is theoretically investigated in the scope of a two-dimensional Holstein-Peierls model that includes lattice relaxation. Particularly, the investigation is focused on designing a model Hamiltonian that can address properly the polaron properties in different model oligoacene crystals. The findings showed that a suitable choice for a set of parameters can play the role of distinguishing the model crystals and, consequently, different properties related to the polaron stability in these systems are observed. Importantly, the usefulness of this model is stressed by investigating the electronic localization of the polaron, which provides a deeper understanding into the properties associated with the polaron stability in oligoacene crystals.

show abstract

Quantum dynamics of a vibronically coupled linear chain using a surrogate Hamiltonian approach

Cited by 6 publications

References 101 publications

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

Electronic energy transfer through non-adiabatic vibrational-electronic resonance. I. Theory for a dimer

Vibronic enhancement of excitation energy transport: Interplay between local and non-local exciton-phonon interactions

Polaron stability in oligoacene crystals

Contact Info

Product

Resources

About