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Understanding Covalent versus Spin–Orbit Coupling Contributions to Temperature-Dependent Electron Spin Relaxation in Cupric and Vanadyl Phthalocyanines

Follmer, Alec H. and Ribson, Ryan D. and Oyala, Paul H. and Chen, Grace Y. and Hadt, Ryan G. (2020) Understanding Covalent versus Spin–Orbit Coupling Contributions to Temperature-Dependent Electron Spin Relaxation in Cupric and Vanadyl Phthalocyanines. Journal of Physical Chemistry A, 124 (44). pp. 9252-9260. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20201028-153430407

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Abstract

Recent interest in transition-metal complexes as potential quantum bits (qubits) has reinvigorated the investigation of fundamental contributions to electron spin relaxation in various ligand scaffolds. From quantum computers to chemical and biological sensors, interest in leveraging the quantum properties of these molecules has opened a discussion of the requirements to maintain coherence over a large temperature range, including near room temperature. Here we compare temperature-, magnetic field position-, and concentration-dependent electron spin relaxation in copper(II) phthalocyanine (CuPc) and vanadyl phthalocyanine (VOPc) doped into diamagnetic hosts. While VOPc demonstrates coherence up to room temperature, CuPc coherence times become rapidly T₁-limited with increasing temperature, despite featuring a more covalent ground-state wave function than VOPc. As rationalized by a ligand field model, this difference is ascribed to different spin–orbit coupling (SOC) constants for Cu(II) versus V(IV). The manifestation of SOC contributions to spin–phonon coupling and electron spin relaxation in different ligand fields is discussed, allowing for a further understanding of the competing roles of SOC and covalency in electron spin relaxation.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpca.0c07860DOIArticle
ORCID:
AuthorORCID
Follmer, Alec H.0000-0002-6244-6804
Oyala, Paul H.0000-0002-8761-4667
Chen, Grace Y.0000-0002-6899-5943
Hadt, Ryan G.0000-0001-6026-1358
Additional Information:© 2020 American Chemical Society. Received: August 28, 2020; Revised: October 15, 2020; Published: October 28, 2020. The Caltech EPR Facility acknowledges support from the NSF (MRI grant 1531940) and the Dow Next Generation Educator Fund. G.Y.C. acknowledges funding through a Johnson & Johnson WAVE fellowship at Caltech. We acknowledge several helpful reviewer comments in the process of revision. Financial support from Caltech and the Dow Next Generation Educator Fund is gratefully acknowledged. Author Contributions: A.H.F. and R.D.R. co-first author. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1531940
Dow Next Generation Educator FundUNSPECIFIED
Johnson & Johnson WAVE FellowshipUNSPECIFIED
CaltechUNSPECIFIED
Issue or Number:44
Record Number:CaltechAUTHORS:20201028-153430407
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20201028-153430407
Official Citation:Understanding Covalent versus Spin–Orbit Coupling Contributions to Temperature-Dependent Electron Spin Relaxation in Cupric and Vanadyl Phthalocyanines. Alec H. Follmer, Ryan D. Ribson, Paul H. Oyala, Grace Y. Chen, and Ryan G. Hadt. The Journal of Physical Chemistry A 2020 124 (44), 9252-9260; DOI: 10.1021/acs.jpca.0c07860
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106342
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Oct 2020 15:44
Last Modified:19 Nov 2020 18:41

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