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Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation

Nonradiative electron–hole (e–h) recombination is the primary source of energy loss in photovoltaic cells and inevitably, it competes with the charge transfer process, leading to poor device performance. Therefore, much attention has to be paid for delaying such processes; increasing the excitonic l...

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Autores principales: Sarkar, Ritabrata, Habib, Md, Kar, Moumita, Pramanik, Anup, Pal, Sougata, Sarkar, Pranab
Formato: Online Artículo Texto
Lenguaje:English
Publicado: RSC 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9419611/
https://www.ncbi.nlm.nih.gov/pubmed/36132296
http://dx.doi.org/10.1039/d0na00001a
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author Sarkar, Ritabrata
Habib, Md
Kar, Moumita
Pramanik, Anup
Pal, Sougata
Sarkar, Pranab
author_facet Sarkar, Ritabrata
Habib, Md
Kar, Moumita
Pramanik, Anup
Pal, Sougata
Sarkar, Pranab
author_sort Sarkar, Ritabrata
collection PubMed
description Nonradiative electron–hole (e–h) recombination is the primary source of energy loss in photovoltaic cells and inevitably, it competes with the charge transfer process, leading to poor device performance. Therefore, much attention has to be paid for delaying such processes; increasing the excitonic lifetime may be a solution for this. Using the real-time, density functional tight-binding theory (DFTB) combined with nonadiabatic molecular dynamics (NAMD) simulations, we demonstrate the exciton relaxation phenomena of different metal-centered porphyrin nanoballs, which are supposed to be very important for the light-harvesting process. It has been revealed that the carrier recombination rate gradually decreases with the increase in the molecular stiffness by introducing metal-coordinating templating agents into the nanoball. Our simulation demonstrates that the lower atomic fluctuations lead to poorer electron–phonon nonadiabatic coupling in association with weak phonon modes and these as a whole are responsible for shorter quantum coherence and hence delayed recombination events. Our analysis is in good agreement with the recent experimental observation. By replacing the Zn metal center with a heavier Cd atom, a similar trend is observed; however, the rate slows down abruptly. The present simulation study provides the fundamental mechanism in detail behind the undesired energy loss during exciton recombination and suggests a rational design of impressive nanosystems for future device fabrication.
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spelling pubmed-94196112022-09-20 Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation Sarkar, Ritabrata Habib, Md Kar, Moumita Pramanik, Anup Pal, Sougata Sarkar, Pranab Nanoscale Adv Chemistry Nonradiative electron–hole (e–h) recombination is the primary source of energy loss in photovoltaic cells and inevitably, it competes with the charge transfer process, leading to poor device performance. Therefore, much attention has to be paid for delaying such processes; increasing the excitonic lifetime may be a solution for this. Using the real-time, density functional tight-binding theory (DFTB) combined with nonadiabatic molecular dynamics (NAMD) simulations, we demonstrate the exciton relaxation phenomena of different metal-centered porphyrin nanoballs, which are supposed to be very important for the light-harvesting process. It has been revealed that the carrier recombination rate gradually decreases with the increase in the molecular stiffness by introducing metal-coordinating templating agents into the nanoball. Our simulation demonstrates that the lower atomic fluctuations lead to poorer electron–phonon nonadiabatic coupling in association with weak phonon modes and these as a whole are responsible for shorter quantum coherence and hence delayed recombination events. Our analysis is in good agreement with the recent experimental observation. By replacing the Zn metal center with a heavier Cd atom, a similar trend is observed; however, the rate slows down abruptly. The present simulation study provides the fundamental mechanism in detail behind the undesired energy loss during exciton recombination and suggests a rational design of impressive nanosystems for future device fabrication. RSC 2020-02-18 /pmc/articles/PMC9419611/ /pubmed/36132296 http://dx.doi.org/10.1039/d0na00001a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Sarkar, Ritabrata
Habib, Md
Kar, Moumita
Pramanik, Anup
Pal, Sougata
Sarkar, Pranab
Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
title Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
title_full Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
title_fullStr Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
title_full_unstemmed Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
title_short Structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
title_sort structural rigidity accelerates quantum decoherence and extends carrier lifetime in porphyrin nanoballs: a time domain atomistic simulation
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9419611/
https://www.ncbi.nlm.nih.gov/pubmed/36132296
http://dx.doi.org/10.1039/d0na00001a
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