Design Rules to Maximize Charge-Carrier Mobility along Conjugated Polymer Chains

Prodhan, Suryoday; Qiu, Jing; Ricci, Matteo; Roscioni, Otello Maria; Wang, Linjun; Beljonne, David

doi:10.1021/acs.jpclett.0c01793

“…In comparison, FSSH forces the nuclei to move on an active PES at any time and allows stochastic surface hops between PESs according to the nonadiabatic coupling. As a result, FSSH can take into account the different motion of nuclear wave packets (WPs) on different PESs.FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an…”

mentioning

confidence: 99%

“…FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an…”

mentioning

confidence: 99%

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Xu

¹

,

Wang

²

2020

J. Phys. Chem. Lett.

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When describing nonadiabatic dynamics based on trajectories, severe trajectory branching occurs when the nuclear wave packets on some potential energy surfaces are reflected while those on the remaining surfaces are not. As a result, the traditional Ehrenfest mean field (EMF) approximation breaks down. In this study, two versions of the branching corrected mean field (BCMF) method are proposed. Namely, when trajectory branching is identified, BCMF stochastically selects either the reflected or the non-reflected group to build the new mean field trajectory or splits the mean field trajectory into two new trajectories with the corresponding weights. As benchmarked in six standard model systems and an extensive model base with two hundred diverse scattering models, BCMF significantly improves the accuracy while retaining the high efficiency of the traditional EMF. In fact, BCMF closely reproduces the exact quantum dynamics in all investigated systems, thus highlighting the essential role of branching correction in nonadiabatic dynamics simulations of general systems. 2Nonadiabatic dynamics have attracted substantial interest in the past decades.Many important phenomena in chemistry, physics, biology, and material sciences (e.g., proton transfer, 1,2 photoisomerization, 3,4 charge transport, 5,6 exciton dissociation, 7,8 and nonradiative energy relaxation 9,10 ) all fall into the category of nonadiabatic dynamics.Compared with adiabatic dynamics, nonadiabatic dynamics involve strongly coupled electronic and nuclear motion, and thus are generally difficult to deal with theoretically.The fully quantum simulations give accurate description but are normally too expensive to carry out in complex systems. Comparatively, mixed quantum-classical dynamics (MQCD) methods are widely utilized due to the potentially good balance between efficiency and reliability. Nowadays, the Ehrenfest mean field (EMF), 11 Tully's fewest switches surface hopping (FSSH), 12 and their many variants have become the most popular approaches for nonadiabatic dynamics simulations in different fields. [13][14][15][16][17][18][19][20] Both EMF and FSSH utilize the time-dependent Schrödinger equation (TDSE) to characterize the electronic wavefunction evolution. 11,12 Their major difference lies in the description of nuclear motion. In EMF, the nuclei evolve on a single effective potential energy surface (PES), which is obtained through averaging over all the electronic states and using the quantum populations as weights. In comparison, FSSH forces the nuclei to move on an active PES at any time and allows stochastic surface hops between PESs according to the nonadiabatic coupling. As a result, FSSH can take into account the different motion of nuclear wave packets (WPs) on different PESs.FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an

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“…In comparison, FSSH forces the nuclei to move on an active PES at any time and allows stochastic surface hops between PESs according to the nonadiabatic coupling. As a result, FSSH can take into account the different motion of nuclear wave packets (WPs) on different PESs.FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an…”

mentioning

confidence: 99%

“…FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an…”

mentioning

confidence: 99%

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Xu¹,

Wang²

2020

Preprint

Self Cite

0

View full text Add to dashboard Cite

When describing nonadiabatic dynamics based on trajectories, severe trajectory branching occurs when the nuclear wave packets on some potential energy surfaces are reflected while those on the remaining surfaces are not. As a result, the traditional Ehrenfest mean field (EMF) approximation breaks down. In this study, two versions of the branching corrected mean field (BCMF) method are proposed. Namely, when trajectory branching is identified, BCMF stochastically selects either the reflected or the non-reflected group to build the new mean field trajectory or splits the mean field trajectory into two new trajectories with the corresponding weights. As benchmarked in six standard model systems and an extensive model base with two hundred diverse scattering models, BCMF significantly improves the accuracy while retaining the high efficiency of the traditional EMF. In fact, BCMF closely reproduces the exact quantum dynamics in all investigated systems, thus highlighting the essential role of branching correction in nonadiabatic dynamics simulations of general systems.

show abstract

“…FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an important role in the great success of the trajectory surface hopping (TSH) approach for nonadiabatic dynamics simulations.…”

mentioning

confidence: 99%

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Xu

¹

,

Wang

²

2020

Preprint

Self Cite

0

View full text Add to dashboard Cite

When describing nonadiabatic dynamics based on trajectories, severe trajectory branching occurs when the nuclear wave packets on some potential energy surfaces are reflected while those on the remaining surfaces are not. As a result, the traditional Ehrenfest mean field (EMF) approximation breaks down. In this study, two versions of the branching corrected mean field (BCMF) method are proposed. Namely, when trajectory branching is identified, BCMF stochastically selects either the reflected or the non-reflected group to build the new mean field trajectory or splits the mean field trajectory into two new trajectories with the corresponding weights. As benchmarked in six standard model systems and an extensive model base with two hundred diverse scattering models, BCMF significantly improves the accuracy while retaining the high efficiency of the traditional EMF. In fact, BCMF closely reproduces the exact quantum dynamics in all investigated systems, thus highlighting the essential role of branching correction in nonadiabatic dynamics simulations of general systems.

show abstract

Design Rules to Maximize Charge-Carrier Mobility along Conjugated Polymer Chains

Cited by 41 publications

References 47 publications

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

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