Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium

We report the spin dynamic properties of non-substituted ferrocenium complexes. Ferrocenium shows a field-induced single-molecule magnet behaviour in DMF solution while cobaltocene lacks slow spin relaxation neither in powder nor in solution. Multireference quantum mechanical calculations give a non...

Descripción completa

Detalles Bibliográficos
Autores: Amoza, Martín, Maxwell, Lindley, Aliaga Alcalde, Nuria, Gómez-Coca, Silvia, Ruiz, Eliseo
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/264270
Acceso en línea:http://hdl.handle.net/10261/264270
https://api.elsevier.com/content/abstract/scopus_id/85118224655
Access Level:acceso abierto
Palabra clave:Ab initio calculations
Magnetic properties
Metallocenes
Spin dynamics
Spin-phonon coupling
id ES_05fa7edd6758b36b579dba6933755d64
oai_identifier_str oai:digital.csic.es:10261/264270
network_acronym_str ES
network_name_str España
repository_id_str
spelling Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine FerroceniumAmoza, MartínMaxwell, LindleyAliaga Alcalde, NuriaGómez-Coca, SilviaRuiz, EliseoAb initio calculationsMagnetic propertiesMetallocenesSpin dynamicsSpin-phonon couplingWe report the spin dynamic properties of non-substituted ferrocenium complexes. Ferrocenium shows a field-induced single-molecule magnet behaviour in DMF solution while cobaltocene lacks slow spin relaxation neither in powder nor in solution. Multireference quantum mechanical calculations give a non-Aufbau orbital occupation for ferrocenium with small first excitation energy that agrees with the relatively large measured magnetic anisotropy for a transition metal S=1/2 system. The analysis of the spin relaxation shows an important participation of quantum tunnelling, Raman, direct and local-mode mechanisms which depend on temperature and the external field conditions. The calculation of spin-phonon coupling constants for the vibrational modes shows that the first vibrational mode, despite having a low spin-phonon constant, is the most efficient process for the spin relaxation at low temperatures. In such conditions, vibrational modes with higher spin-phonon coupling constants are not populated. Additionally, the vibrational energy of this first mode is in excellent agreement with the experimental fitted value obtained from the local-mode mechanism.The research reported here was supported by the Spanish Ministerio de Ciencia, Innovación y Universidades (grants PGC2018-093863-B-C21, PID2019-108794GB-I00 and centres of excellence MDM-2017-0767 and Severo Ochoa FUNFUTURE (CEX2019-000917-S). E.R. thanks Generalitat de Catalunya for an ICREA Academia award and for the SGR2017-1289 and -1277 grants. S.G.-C. thanks the Generalitat de Catalunya for a Beatriu de Pinòs grant. M.A. acknowledges the Ministerio de Educación, Cultura y Deporte for an FPU predoctoral grant. Authors acknowledge computer resources, technical expertise and assistance provided by the CSUC. We want to thank Prof. Santiago Alvarez for his help with the Shape code.With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).Peer reviewedWiley-VCHMinisterio de Ciencia, Innovación y Universidades (España)Generalitat de CatalunyaAliaga Alcalde, Nuria [0000-0003-1080-3862]Gómez-Coca, Silvia [0000-0002-2299-4697]Ruiz, Eliseo [0000-0001-9097-8499]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202220222021info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/264270https://api.elsevier.com/content/abstract/scopus_id/85118224655reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-093863-B-C21info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-108794GB-I00info:eu-repo/grantAgreement/MICIU/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/MDM-2017-0767info:eu-repo/grantAgreement/MICIU/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-SChemistry (Weinheim an der Bergstrasse, Germany)http://dx.doi.org/10.1002/chem.202102603Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2642702026-05-22T06:33:51Z
dc.title.none.fl_str_mv Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
title Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
spellingShingle Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
Amoza, Martín
Ab initio calculations
Magnetic properties
Metallocenes
Spin dynamics
Spin-phonon coupling
title_short Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
title_full Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
title_fullStr Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
title_full_unstemmed Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
title_sort Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium
dc.creator.none.fl_str_mv Amoza, Martín
Maxwell, Lindley
Aliaga Alcalde, Nuria
Gómez-Coca, Silvia
Ruiz, Eliseo
author Amoza, Martín
author_facet Amoza, Martín
Maxwell, Lindley
Aliaga Alcalde, Nuria
Gómez-Coca, Silvia
Ruiz, Eliseo
author_role author
author2 Maxwell, Lindley
Aliaga Alcalde, Nuria
Gómez-Coca, Silvia
Ruiz, Eliseo
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia, Innovación y Universidades (España)
Generalitat de Catalunya
Aliaga Alcalde, Nuria [0000-0003-1080-3862]
Gómez-Coca, Silvia [0000-0002-2299-4697]
Ruiz, Eliseo [0000-0001-9097-8499]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Ab initio calculations
Magnetic properties
Metallocenes
Spin dynamics
Spin-phonon coupling
topic Ab initio calculations
Magnetic properties
Metallocenes
Spin dynamics
Spin-phonon coupling
description We report the spin dynamic properties of non-substituted ferrocenium complexes. Ferrocenium shows a field-induced single-molecule magnet behaviour in DMF solution while cobaltocene lacks slow spin relaxation neither in powder nor in solution. Multireference quantum mechanical calculations give a non-Aufbau orbital occupation for ferrocenium with small first excitation energy that agrees with the relatively large measured magnetic anisotropy for a transition metal S=1/2 system. The analysis of the spin relaxation shows an important participation of quantum tunnelling, Raman, direct and local-mode mechanisms which depend on temperature and the external field conditions. The calculation of spin-phonon coupling constants for the vibrational modes shows that the first vibrational mode, despite having a low spin-phonon constant, is the most efficient process for the spin relaxation at low temperatures. In such conditions, vibrational modes with higher spin-phonon coupling constants are not populated. Additionally, the vibrational energy of this first mode is in excellent agreement with the experimental fitted value obtained from the local-mode mechanism.
publishDate 2021
dc.date.none.fl_str_mv 2021
2022
2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/264270
https://api.elsevier.com/content/abstract/scopus_id/85118224655
url http://hdl.handle.net/10261/264270
https://api.elsevier.com/content/abstract/scopus_id/85118224655
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-093863-B-C21
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-108794GB-I00
info:eu-repo/grantAgreement/MICIU/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/MDM-2017-0767
info:eu-repo/grantAgreement/MICIU/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-S
Chemistry (Weinheim an der Bergstrasse, Germany)
http://dx.doi.org/10.1002/chem.202102603
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869402889235988480
score 15,811543

Similares en LA Referencia