Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

Dergachev, Vsevolod D.; Nakritskaia, Daria D.; Varganov, Sergey A.

doi:10.1021/acs.jpclett.2c01627

Title: Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

Journal Article · 18 July 2022 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.2c01627 · OSTI ID:1899421

Dergachev, Vsevolod D. ^[1]; Nakritskaia, Daria D. ^[2];

^[2]

Univ. of Nevada, Reno, NV (United States); University of Nevada, Reno
Univ. of Nevada, Reno, NV (United States)

Lanthanide-based single-molecule magnets (SMMs) are promising building blocks for quantum memory and spintronic devices. Designing lanthanide-based SMMs with long spin relaxation time requires a detailed understanding of their electronic structure, including the crucial role of the spin-orbit coupling (SOC). While traditional calculations of SOC using the perturbation theory applied to a solution of the non-relativistic Schrödinger equation are valid for light atoms, this approach is questionable for systems containing heavy elements such as lanthanides. We investigate the accuracy of the perturbation estimates of SOC by variationally solving the Dirac equation for the [DyO]⁺ molecule, a prototype of a lanthanide-based SMM. We show that the energy splittings between the M_J states involved in spin relaxation depend on the interplay between strong SOC and dynamic electron correlations. Here, we demonstrate that this interplay affects the resonances between the spin and vibrational transitions, and, therefore, the spin relaxation time.

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Research Organization:: Univ. of Nevada, Reno, NV (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022178

OSTI ID:: 1899421

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 29 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Ab Initio Crystal Field for Lanthanides Ungur, Liviu; Chibotaru, Liviu F. Chemistry - A European Journal, Vol. 23, Issue 15 https://doi.org/10.1002/chem.201605102	journal	February 2017
Relativistic Hamiltonians for Chemistry: A Primer Saue, Trond ChemPhysChem, Vol. 12, Issue 17 https://doi.org/10.1002/cphc.201100682	journal	November 2011
Dependence of relativistic effects on electronic configuration in the neutral atoms of d- and f-block elements Autschbach, J.; Siekierski, S.; Seth, M. Journal of Computational Chemistry, Vol. 23, Issue 8 https://doi.org/10.1002/jcc.10060	journal	April 2002
General atomic and molecular electronic structure system Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A. Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363 https://doi.org/10.1002/jcc.540141112	journal	November 1993
Nonadiabatic transition state theory: Application to intersystem crossings in the active sites of metal-sulfur proteins Lykhin, Aleksandr O.; Kaliakin, Danil S.; dePolo, Gwen E. International Journal of Quantum Chemistry, Vol. 116, Issue 10 https://doi.org/10.1002/qua.25124	journal	March 2016
Spin-orbit coupling and intersystem crossing in molecules: Spin-orbit coupling Marian, Christel M. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.83	journal	July 2011
Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the lanthanides La–Lu Gomes, André S. P.; Dyall, Kenneth G.; Visscher, Lucas Theoretical Chemistry Accounts, Vol. 127, Issue 4 https://doi.org/10.1007/s00214-009-0725-7	journal	January 2010
Ten Years of Glory in the α-Functionalizations of Acetophenones: Progress Through Kornblum Oxidation and C–H Functionalization Deka, Bhaskar; Rastogi, Gaurav K.; Deb, Mohit L. Topics in Current Chemistry, Vol. 380, Issue 1 https://doi.org/10.1007/s41061-021-00356-4	journal	November 2021
The multi-state CASPT2 method Finley, James; Malmqvist, Per-Åke; Roos, Björn O. Chemical Physics Letters, Vol. 288, Issue 2-4 https://doi.org/10.1016/S0009-2614(98)00252-8	journal	May 1998
Two-component methods of relativistic quantum chemistry: from the Douglas–Kroll approximation to the exact two-component formalism Barysz, Maria; Sadlej, Andrzej J. Journal of Molecular Structure: THEOCHEM, Vol. 573, Issue 1-3 https://doi.org/10.1016/S0166-1280(01)00542-5	journal	October 2001
Molecular magnetism of lanthanide: Advances and perspectives Zhu, Zhenhua; Guo, Mei; Li, Xiao-Lei Coordination Chemistry Reviews, Vol. 378 https://doi.org/10.1016/j.ccr.2017.10.030	journal	January 2019
Strategies toward High-Temperature Lanthanide-Based Single-Molecule Magnets Ungur, Liviu; Chibotaru, Liviu F. Inorganic Chemistry, Vol. 55, Issue 20 https://doi.org/10.1021/acs.inorgchem.6b01353	journal	August 2016
Relativistic Effects in Modeling the Ligand K-Edge X-ray Absorption Near-Edge Structure of Uranium Complexes Kasper, Joseph M.; Li, Xiaosong; Kozimor, Stosh A. Journal of Chemical Theory and Computation, Vol. 18, Issue 4 https://doi.org/10.1021/acs.jctc.1c00851	journal	March 2022
Relativistic Two-Component Multireference Configuration Interaction Method with Tunable Correlation Space Hu, Hang; Jenkins, Andrew J.; Liu, Hongbin Journal of Chemical Theory and Computation, Vol. 16, Issue 5 https://doi.org/10.1021/acs.jctc.9b01290	journal	April 2020
Intersystem Crossings in Late-Row Elements: A Perspective Valentine, Andrew J. S.; Li, Xiaosong The Journal of Physical Chemistry Letters, Vol. 13, Issue 13 https://doi.org/10.1021/acs.jpclett.2c00207	journal	March 2022
In Silico Molecular Engineering of Dysprosocenium-Based Complexes to Decouple Spin Energy Levels from Molecular Vibrations Ullah, Aman; Cerdá, Jesús; Baldoví, José J. The Journal of Physical Chemistry Letters, Vol. 10, Issue 24 https://doi.org/10.1021/acs.jpclett.9b02982	journal	November 2019
Ab Initio Prediction of High-Temperature Magnetic Relaxation Rates in Single-Molecule Magnets Reta, Daniel; Kragskow, Jon G. C.; Chilton, Nicholas F. Journal of the American Chemical Society, Vol. 143, Issue 15 https://doi.org/10.1021/jacs.1c01410	journal	April 2021
A Complete Ab Initio View of Orbach and Raman Spin–Lattice Relaxation in a Dysprosium Coordination Compound Briganti, Matteo; Santanni, Fabio; Tesi, Lorenzo Journal of the American Chemical Society, Vol. 143, Issue 34 https://doi.org/10.1021/jacs.1c05068	journal	August 2021
New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF ₃ Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke The Journal of Physical Chemistry A, Vol. 112, Issue 45 https://doi.org/10.1021/jp803213j	journal	November 2008
Quantum computing in molecular magnets Leuenberger, Michael N.; Loss, Daniel Nature, Vol. 410, Issue 6830 https://doi.org/10.1038/35071024	journal	April 2001
Spin–orbit coupling in quantum gases Galitski, Victor; Spielman, Ian B. Nature, Vol. 494, Issue 7435 https://doi.org/10.1038/nature11841	journal	February 2013
Molecular magnetic hysteresis at 60 kelvin in dysprosocenium Goodwin, Conrad A. P.; Ortu, Fabrizio; Reta, Daniel Nature, Vol. 548, Issue 7668 https://doi.org/10.1038/nature23447	journal	August 2017
Towards molecular spintronics Rocha, Alexandre R.; García-suárez, Víctor M.; Bailey, Steve W. Nature Materials, Vol. 4, Issue 4 https://doi.org/10.1038/nmat1349	journal	March 2005
Molecular spintronics using single-molecule magnets Bogani, Lapo; Wernsdorfer, Wolfgang Nature Materials, Vol. 7, Issue 3 https://doi.org/10.1038/nmat2133	journal	March 2008
Magnetic memory of a single-molecule quantum magnet wired to a gold surface Mannini, Matteo; Pineider, Francesco; Sainctavit, Philippe Nature Materials, Vol. 8, Issue 3 https://doi.org/10.1038/nmat2374	journal	February 2009
Relativistic quantum chemical calculations show that the uranium molecule U2 has a quadruple bond Knecht, Stefan; Jensen, Hans Jørgen Aa.; Saue, Trond Nature Chemistry, Vol. 11, Issue 1 https://doi.org/10.1038/s41557-018-0158-9	journal	October 2018
The periodic table and the physics that drives it Schwerdtfeger, Peter; Smits, Odile R.; Pyykkö, Pekka Nature Reviews Chemistry, Vol. 4, Issue 7 https://doi.org/10.1038/s41570-020-0195-y	journal	June 2020
Combining the spin-separated exact two-component relativistic Hamiltonian with the equation-of-motion coupled-cluster method for the treatment of spin–orbit splittings of light and heavy elements Cao, Zhanli; Li, Zhendong; Wang, Fan Physical Chemistry Chemical Physics, Vol. 19, Issue 5 https://doi.org/10.1039/C6CP07588F	journal	January 2017
A method to predict both the relaxation time of quantum tunneling of magnetization and the effective barrier of magnetic reversal for a Kramers single-ion magnet Yin, Bing; Li, Chao-Chao Physical Chemistry Chemical Physics, Vol. 22, Issue 18 https://doi.org/10.1039/D0CP00933D	journal	January 2020
The anisotropy of the internal magnetic field on the central ion is capable of imposing great impact on the quantum tunneling of magnetization of Kramers single-ion magnets Yin, Bing; Luo, Lan Physical Chemistry Chemical Physics, Vol. 23, Issue 4 https://doi.org/10.1039/D0CP05470D	journal	January 2021
Spin dynamics in single-molecule magnets and molecular qubits Aravena, Daniel; Ruiz, Eliseo Dalton Transactions, Vol. 49, Issue 29 https://doi.org/10.1039/D0DT01414A	journal	January 2020
Magnetic anisotropy in the excited states of low symmetry lanthanide complexes Ungur, Liviu; Chibotaru, Liviu F. Physical Chemistry Chemical Physics, Vol. 13, Issue 45 https://doi.org/10.1039/c1cp22689d	journal	January 2011
Exploiting single-ion anisotropy in the design of f-element single-molecule magnets Rinehart, Jeffrey D.; Long, Jeffrey R. Chemical Science, Vol. 2, Issue 11 https://doi.org/10.1039/c1sc00513h	journal	January 2011
Infinite-order two-component theory for relativistic quantum chemistry Barysz, Maria; Sadlej, Andrzej J. The Journal of Chemical Physics, Vol. 116, Issue 7 https://doi.org/10.1063/1.1436462	journal	February 2002
An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation Iliaš, Miroslav; Saue, Trond The Journal of Chemical Physics, Vol. 126, Issue 6 https://doi.org/10.1063/1.2436882	journal	February 2007
Exact two-component Hamiltonians revisited Liu, Wenjian; Peng, Daoling The Journal of Chemical Physics, Vol. 131, Issue 3 https://doi.org/10.1063/1.3159445	journal	July 2009
Time-dependent approaches for the calculation of intersystem crossing rates Etinski, Mihajlo; Tatchen, Jörg; Marian, Christel M. The Journal of Chemical Physics, Vol. 134, Issue 15 https://doi.org/10.1063/1.3575582	journal	April 2011
Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory Granovsky, Alexander A. The Journal of Chemical Physics, Vol. 134, Issue 21 https://doi.org/10.1063/1.3596699	journal	June 2011
A new internally contracted multi-reference configuration interaction method Shamasundar, K. R.; Knizia, Gerald; Werner, Hans-Joachim The Journal of Chemical Physics, Vol. 135, Issue 5 https://doi.org/10.1063/1.3609809	journal	August 2011
Perspective: Relativistic effects Autschbach, Jochen The Journal of Chemical Physics, Vol. 136, Issue 15 https://doi.org/10.1063/1.3702628	journal	April 2012
Relativistic four‐component multiconfigurational self‐consistent‐field theory for molecules: Formalism Jo/rgen Aa. Jensen, Hans; Dyall, Kenneth G.; Saue, Trond The Journal of Chemical Physics, Vol. 104, Issue 11 https://doi.org/10.1063/1.471644	journal	March 1996
Local unitary transformation method for large-scale two-component relativistic calculations: Case for a one-electron Dirac Hamiltonian Seino, Junji; Nakai, Hiromi The Journal of Chemical Physics, Vol. 136, Issue 24 https://doi.org/10.1063/1.4729463	journal	June 2012
Local unitary transformation method for large-scale two-component relativistic calculations. II. Extension to two-electron Coulomb interaction Seino, Junji; Nakai, Hiromi The Journal of Chemical Physics, Vol. 137, Issue 14 https://doi.org/10.1063/1.4757263	journal	October 2012
Modern quantum chemistry with [Open]Molcas Aquilante, Francesco; Autschbach, Jochen; Baiardi, Alberto The Journal of Chemical Physics, Vol. 152, Issue 21 https://doi.org/10.1063/5.0004835	journal	June 2020
The DIRAC code for relativistic molecular calculations Saue, Trond; Bast, Radovan; Gomes, André Severo Pereira The Journal of Chemical Physics, Vol. 152, Issue 20 https://doi.org/10.1063/5.0004844	journal	May 2020
Spin-orbit coupling in molecules: Chemistry beyond the adiabatic approximation Fedorov, Dmitri G.; Koseki, Shiro; Schmidt, Michael W. International Reviews in Physical Chemistry, Vol. 22, Issue 3 https://doi.org/10.1080/0144235032000101743	journal	July 2003
Fermi’s golden rule: its derivation and breakdown by an ideal model Zhang, J. M.; Liu, Y. European Journal of Physics, Vol. 37, Issue 6 https://doi.org/10.1088/0143-0807/37/6/065406	journal	October 2016
Molecular Nanomagnets Gatteschi, Dante; Sessoli, Roberta; Villain, Jacques https://doi.org/10.1093/acprof:oso/9780198567530.001.0001	book	January 2006
Understanding magnetic relaxation in single-ion magnets with high blocking temperature Chiesa, A.; Cugini, F.; Hussain, R. Physical Review B, Vol. 101, Issue 17 https://doi.org/10.1103/PhysRevB.101.174402	journal	May 2020
Molecular spintronics using single-molecule magnets under irradiation Hymas, Kieran; Soncini, Alessandro Physical Review B, Vol. 99, Issue 24 https://doi.org/10.1103/PhysRevB.99.245404	journal	June 2019
Spintronics: Fundamentals and applications Žutić, Igor; Fabian, Jaroslav; Das Sarma, S. Reviews of Modern Physics, Vol. 76, Issue 2 https://doi.org/10.1103/RevModPhys.76.323	journal	April 2004
How do phonons relax molecular spins? Lunghi, Alessandro; Sanvito, Stefano Science Advances, Vol. 5, Issue 9 https://doi.org/10.1126/sciadv.aax7163	journal	September 2019
Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet Guo, Fu-Sheng; Day, Benjamin M.; Chen, Yan-Cong Science, Vol. 362, Issue 6421 https://doi.org/10.1126/science.aav0652	journal	October 2018
Ultrahard magnetism from mixed-valence dilanthanide complexes with metal-metal bonding Gould, Colin A.; McClain, K. Randall; Reta, Daniel Science, Vol. 375, Issue 6577 https://doi.org/10.1126/science.abl5470	journal	January 2022
Understanding and Controlling Intersystem Crossing in Molecules Marian, Christel M. Annual Review of Physical Chemistry, Vol. 72, Issue 1 https://doi.org/10.1146/annurev-physchem-061020-053433	journal	April 2021

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Title: Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

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