Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/101243 https://doi.org/10.1039/d1cp00076d |
Resumo: | In 1975, Buchwalter and Closs reported one of the first examples of heavy-atom quantum mechanical tunneling (QMT) by studying the ring closure of triplet cyclopentane-1,3-diyl to singlet bicyclo[2.1.0]pentane in cryogenic glasses. Since then, no clear theoretical evidence has been provided to elucidate how the intersystem crossing (ISC) and QMT are related in the reaction mechanism. In this work, we unequivocally show that at cryogenic temperatures, the ISC occurs solely in the quantum tunneling regime, with weak coupling non-adiabatic transition state theory rate constants predicting a spontaneous reaction in fair agreement with experimental observations. Despite its limitations, such an approach can be used to help unlock a comprehensive understanding of a variety of spin-forbidden chemical reactions in the low temperature regime. |
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Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diylIn 1975, Buchwalter and Closs reported one of the first examples of heavy-atom quantum mechanical tunneling (QMT) by studying the ring closure of triplet cyclopentane-1,3-diyl to singlet bicyclo[2.1.0]pentane in cryogenic glasses. Since then, no clear theoretical evidence has been provided to elucidate how the intersystem crossing (ISC) and QMT are related in the reaction mechanism. In this work, we unequivocally show that at cryogenic temperatures, the ISC occurs solely in the quantum tunneling regime, with weak coupling non-adiabatic transition state theory rate constants predicting a spontaneous reaction in fair agreement with experimental observations. Despite its limitations, such an approach can be used to help unlock a comprehensive understanding of a variety of spin-forbidden chemical reactions in the low temperature regime.Royal Society of Chemistry2021-03-18info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/101243http://hdl.handle.net/10316/101243https://doi.org/10.1039/d1cp00076denghttps://doi.org/10.1039/D1CP00076DViegas, Luís PNunes, Cláudio MFausto, Ruiinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2022-08-17T23:02:11Zoai:estudogeral.uc.pt:10316/101243Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:18:28.503637Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
title |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
spellingShingle |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl Viegas, Luís P |
title_short |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
title_full |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
title_fullStr |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
title_full_unstemmed |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
title_sort |
Spin-forbidden heavy-atom tunneling in the ring-closure of triplet cyclopentane-1,3-diyl |
author |
Viegas, Luís P |
author_facet |
Viegas, Luís P Nunes, Cláudio M Fausto, Rui |
author_role |
author |
author2 |
Nunes, Cláudio M Fausto, Rui |
author2_role |
author author |
dc.contributor.author.fl_str_mv |
Viegas, Luís P Nunes, Cláudio M Fausto, Rui |
description |
In 1975, Buchwalter and Closs reported one of the first examples of heavy-atom quantum mechanical tunneling (QMT) by studying the ring closure of triplet cyclopentane-1,3-diyl to singlet bicyclo[2.1.0]pentane in cryogenic glasses. Since then, no clear theoretical evidence has been provided to elucidate how the intersystem crossing (ISC) and QMT are related in the reaction mechanism. In this work, we unequivocally show that at cryogenic temperatures, the ISC occurs solely in the quantum tunneling regime, with weak coupling non-adiabatic transition state theory rate constants predicting a spontaneous reaction in fair agreement with experimental observations. Despite its limitations, such an approach can be used to help unlock a comprehensive understanding of a variety of spin-forbidden chemical reactions in the low temperature regime. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-03-18 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/101243 http://hdl.handle.net/10316/101243 https://doi.org/10.1039/d1cp00076d |
url |
http://hdl.handle.net/10316/101243 https://doi.org/10.1039/d1cp00076d |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
https://doi.org/10.1039/D1CP00076D |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
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1799134079160942592 |