Unraveling Abnormal Collective Effects via the Non-Monotonic Number Dependence of Electron Transfer in Confined Electromagnetic Fields
Strong light-matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to the possibilities of modifying chemical reactivity and molecular properties. While collective optical responses, such as enhanced Rabi splittin...
Saved in:
Published in | arXiv.org |
---|---|
Main Authors | , |
Format | Paper |
Language | English |
Published |
Ithaca
Cornell University Library, arXiv.org
24.06.2024
|
Subjects | |
Online Access | Get full text |
Cover
Loading…
Abstract | Strong light-matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to the possibilities of modifying chemical reactivity and molecular properties. While collective optical responses, such as enhanced Rabi splitting, are often observed, the overall effect of the cavity on molecular systems remains ambiguous for a large number of molecules. In this paper, we investigate the non-adiabatic electron transfer (ET) process in electron donor-acceptor pairs influenced by collective excitation and local molecular dynamics. Using the timescale difference between reorganization and thermal fluctuations, we derive analytical formulas for the electron transfer rate constant and the polariton relaxation rate. These formulas apply to any number of molecules (\(N\)) and account for the collective effect as induced by cavity photon coupling. Our findings reveal a non-monotonic dependence of the rate constant on \(N\), which can be understood by the interplay between electron transfer and polariton relaxation. As a result, the cavity-induced quantum yield increases linearly with \(N\) for small \(N\) (as predicted by a simple Dicke model), but shows a turnover and suppression for large \(N\) (consistent with the large \(N\) problem of polariton chemistry). We also interrelate the thermal bath frequency and the number of molecules, suggesting the optimal number for maximizing enhancement. The analysis provides an analytical insight for understanding the collective excitation of light and electron transfer, helping to predict the optimal condition for effective cavity-controlled chemical reactivity. |
---|---|
AbstractList | Strong light-matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to the possibilities of modifying chemical reactivity and molecular properties. While collective optical responses, such as enhanced Rabi splitting, are often observed, the overall effect of the cavity on molecular systems remains ambiguous for a large number of molecules. In this paper, we investigate the non-adiabatic electron transfer (ET) process in electron donor-acceptor pairs influenced by collective excitation and local molecular dynamics. Using the timescale difference between reorganization and thermal fluctuations, we derive analytical formulas for the electron transfer rate constant and the polariton relaxation rate. These formulas apply to any number of molecules (\(N\)) and account for the collective effect as induced by cavity photon coupling. Our findings reveal a non-monotonic dependence of the rate constant on \(N\), which can be understood by the interplay between electron transfer and polariton relaxation. As a result, the cavity-induced quantum yield increases linearly with \(N\) for small \(N\) (as predicted by a simple Dicke model), but shows a turnover and suppression for large \(N\) (consistent with the large \(N\) problem of polariton chemistry). We also interrelate the thermal bath frequency and the number of molecules, suggesting the optimal number for maximizing enhancement. The analysis provides an analytical insight for understanding the collective excitation of light and electron transfer, helping to predict the optimal condition for effective cavity-controlled chemical reactivity. |
Author | Sharma, Shravan Kumar Chen, Hsing-Ta |
Author_xml | – sequence: 1 givenname: Shravan surname: Sharma middlename: Kumar fullname: Sharma, Shravan Kumar – sequence: 2 givenname: Hsing-Ta surname: Chen fullname: Chen, Hsing-Ta |
BookMark | eNqNjM1uwjAQhC0EEr_vsFLPkYJNgB4rGsQFTnBGJllTI2eX2k4eoc9dI8Gd04z0zXxj0Scm7ImRVGqerRdSDsUshFue53K5kkWhRuLvRF536Cxd4etC7BvtYMPOYRVth1Aak1qAzmqIPwgHpmzPxJHJVnBomwt6-MY7Uo1UIbCB8vH1THD0moJJ3FJSkrGE9Ys2-koYk2Jr0dVhKgZGu4CzZ07Ex7Y8bnbZ3fNviyGeb9x6Suis8pVUxfJzPVfvrf4B-SZUtQ |
ContentType | Paper |
Copyright | 2024. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License. |
Copyright_xml | – notice: 2024. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License. |
DBID | 8FE 8FG ABJCF ABUWG AFKRA AZQEC BENPR BGLVJ CCPQU DWQXO HCIFZ L6V M7S PIMPY PQEST PQQKQ PQUKI PRINS PTHSS |
DatabaseName | ProQuest SciTech Collection ProQuest Technology Collection Materials Science & Engineering Collection ProQuest Central (Alumni) ProQuest Central ProQuest Central Essentials AUTh Library subscriptions: ProQuest Central Technology Collection ProQuest One Community College ProQuest Central SciTech Premium Collection (Proquest) (PQ_SDU_P3) ProQuest Engineering Collection Engineering Database Publicly Available Content Database ProQuest One Academic Eastern Edition (DO NOT USE) ProQuest One Academic ProQuest One Academic UKI Edition ProQuest Central China Engineering Collection |
DatabaseTitle | Publicly Available Content Database Engineering Database Technology Collection ProQuest Central Essentials ProQuest One Academic Eastern Edition ProQuest Central (Alumni Edition) SciTech Premium Collection ProQuest One Community College ProQuest Technology Collection ProQuest SciTech Collection ProQuest Central China ProQuest Central ProQuest Engineering Collection ProQuest One Academic UKI Edition ProQuest Central Korea Materials Science & Engineering Collection ProQuest One Academic Engineering Collection |
DatabaseTitleList | Publicly Available Content Database |
Database_xml | – sequence: 1 dbid: 8FG name: ProQuest Technology Collection url: https://search.proquest.com/technologycollection1 sourceTypes: Aggregation Database |
DeliveryMethod | fulltext_linktorsrc |
Discipline | Physics |
EISSN | 2331-8422 |
Genre | Working Paper/Pre-Print |
GroupedDBID | 8FE 8FG ABJCF ABUWG AFKRA ALMA_UNASSIGNED_HOLDINGS AZQEC BENPR BGLVJ CCPQU DWQXO FRJ HCIFZ L6V M7S M~E PIMPY PQEST PQQKQ PQUKI PRINS PTHSS |
ID | FETCH-proquest_journals_30723569813 |
IEDL.DBID | 8FG |
IngestDate | Thu Oct 10 20:41:50 EDT 2024 |
IsOpenAccess | true |
IsPeerReviewed | false |
IsScholarly | false |
Language | English |
LinkModel | DirectLink |
MergedId | FETCHMERGED-proquest_journals_30723569813 |
OpenAccessLink | https://www.proquest.com/docview/3072356981?pq-origsite=%requestingapplication% |
PQID | 3072356981 |
PQPubID | 2050157 |
ParticipantIDs | proquest_journals_3072356981 |
PublicationCentury | 2000 |
PublicationDate | 20240624 |
PublicationDateYYYYMMDD | 2024-06-24 |
PublicationDate_xml | – month: 06 year: 2024 text: 20240624 day: 24 |
PublicationDecade | 2020 |
PublicationPlace | Ithaca |
PublicationPlace_xml | – name: Ithaca |
PublicationTitle | arXiv.org |
PublicationYear | 2024 |
Publisher | Cornell University Library, arXiv.org |
Publisher_xml | – name: Cornell University Library, arXiv.org |
SSID | ssj0002672553 |
Score | 3.5543036 |
SecondaryResourceType | preprint |
Snippet | Strong light-matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to... |
SourceID | proquest |
SourceType | Aggregation Database |
SubjectTerms | Electromagnetic fields Electromagnetism Electron transfer Excitation Molecular dynamics Molecular properties Optical properties Optimization Polaritons Thermal baths |
Title | Unraveling Abnormal Collective Effects via the Non-Monotonic Number Dependence of Electron Transfer in Confined Electromagnetic Fields |
URI | https://www.proquest.com/docview/3072356981 |
hasFullText | 1 |
inHoldings | 1 |
isFullTextHit | |
isPrint | |
link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwfV1LSwMxEB60i-DNJz5qGdBrsJts1-5JfOxahC5FLPRWspusFDTbdqtHj_5uM3FXD0KPyUAIIZnHl5n5AC6iIIsICmRCyYgFUvosUlowkeW6K4XieUaA_jANB-PgcdKb1IBbVadVNjrRKWpV5oSRX9q7yEUvjPr-9XzBiDWKfldrCo1N8HzqhEeV4snDL8bCwyvrMYt_atbZjmQHvJGc6-UubGizB1su5TKv9uFrbIj6h8rB8SYz5Du-oovjnQrCn77CFX7MJFovDdPSMPsCyxU1s8XUMXngfc1hm2ssC4xrTht0Fqiw8plBqumzrqRqpG_yxVDlIiaUvFYdwHkSP98NWLP5aX29qunfYYhDaJnS6CNAZSeKgivhU9Cnoj6XUnX7WikpQxUUx9Bet9LJevEpbHNrzylLigdtaK2W7_rM2uNV1nGH3gHvNk5HT3Y0_Iy_Ac7EmXc |
link.rule.ids | 786,790,12792,21416,33406,33777,43633,43838 |
linkProvider | ProQuest |
linkToHtml | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwfV1LSwMxEB60RfTmEx9VB_QabJPtunsSHy1V26VIC72V7CZbCpqt3epP8HebiakehF4zEEIe8_gyMx_AZRykMUGBTCgZs0DKBouVFkykma5LoXiWEqDfS8LOMHgaNUcecCt9WuVSJzpFrYqMMPIrexe5aIZx1LiZvTNijaLfVU-hsQ5VarkZVaB610r6L78oCw-vrc8s_ilaZz3a21Dty5me78CaNruw4ZIus3IPvoaGyH-oIBxvU0Pe4yu6SN4pIfzpLFzi51Si9dMwKQyzb7BYUDtbTByXBz54FttMY5Fjy7PaoLNBuZVPDVJVn3Um1VL6JieGahexTelr5T5ctFuD-w5bLn7sL1g5_tsOcQAVUxh9CKjsQJ5zJRoU9qk44lKqeqSVkjJUQX4EtVUzHa8Wn8NmZ9DrjruPyfMJbHFr3Slnigc1qCzmH_rUWudFeuaP4BtKD5sD |
openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Unraveling+Abnormal+Collective+Effects+via+the+Non-Monotonic+Number+Dependence+of+Electron+Transfer+in+Confined+Electromagnetic+Fields&rft.jtitle=arXiv.org&rft.au=Sharma%2C+Shravan+Kumar&rft.au=Chen%2C+Hsing-Ta&rft.date=2024-06-24&rft.pub=Cornell+University+Library%2C+arXiv.org&rft.eissn=2331-8422 |