DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp iPr5)2 single-molecule magnet

Abstract

Molecular spin qubits with long spin coherence time as well as non-invasive operation methods on such qubits are in high demand. It was shown that both molecular electronic and nuclear spin levels can be used as qubits. In solid state systems with dopants, an electric field was shown to effectively change the spacing between the nuclear spin qubit levels when the electron spin density is high at the nucleus of the dopant. Inspired by such solid-state systems, we propose that divalent lanthanide (Ln) complexes with an unusual electronic configuration of Ln2+ have a strong interaction between the Ln nuclear spin and the electronic degrees of freedom, which renders electrical tuning of the interaction. Furthermore, as an example, we study electronic structure and hyperfine interaction of the 159Tb nucleus in a neutral Tb(II)(CpiPr5)2 single-molecule magnet (SMM), which exhibits unusually long magnetization relaxation time, using the complete active space self-consistent field (CASSCF) method with spin–orbit interaction included within the restricted active space state interaction (RASSI). Our calculations show that the low-energy states arise from 4f8(6s,5dz2)1, 4f8(5dx2-y2)1, and 4f8(5dxy)1 configurations. We compute the hyperfine interaction parameters and the electronic–nuclear spectrum within our multiconfigurational approach. We find that the hyperfine interaction is about onemore » order of magnitude greater than that for Tb(III)Pc2 SMMs. This stems from the strong Fermi contact interaction between the Tb nuclear spin and the electron spin density at the nucleus that originates from the occupation of the (6s,5d) orbitals. We also uncover that the response of the Fermi contact term to electric field results in electrical tuning of the electronic–nuclear level separations. This hyperfine Stark effect may be useful for applications of molecular nuclear spins for quantum computing.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); San Diego Supercomputer Center (SDSC)
OSTI Identifier:
1852594
Alternate Identifier(s):
OSTI ID: 1664580
Grant/Contract Number:  
SC0018326; DMR060009N
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 38; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Smith, Robert L., Wysocki, Aleksander L., and Park, Kyungwha. Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp iPr5)2 single-molecule magnet. United States: N. p., 2020. Web. doi:10.1039/d0cp04056h.
Smith, Robert L., Wysocki, Aleksander L., & Park, Kyungwha. Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp iPr5)2 single-molecule magnet. United States. https://doi.org/10.1039/d0cp04056h
Smith, Robert L., Wysocki, Aleksander L., and Park, Kyungwha. Tue . "Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp iPr5)2 single-molecule magnet". United States. https://doi.org/10.1039/d0cp04056h. https://www.osti.gov/servlets/purl/1852594.
@article{osti_1852594,
title = {Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp iPr5)2 single-molecule magnet},
author = {Smith, Robert L. and Wysocki, Aleksander L. and Park, Kyungwha},
abstractNote = {Molecular spin qubits with long spin coherence time as well as non-invasive operation methods on such qubits are in high demand. It was shown that both molecular electronic and nuclear spin levels can be used as qubits. In solid state systems with dopants, an electric field was shown to effectively change the spacing between the nuclear spin qubit levels when the electron spin density is high at the nucleus of the dopant. Inspired by such solid-state systems, we propose that divalent lanthanide (Ln) complexes with an unusual electronic configuration of Ln2+ have a strong interaction between the Ln nuclear spin and the electronic degrees of freedom, which renders electrical tuning of the interaction. Furthermore, as an example, we study electronic structure and hyperfine interaction of the 159Tb nucleus in a neutral Tb(II)(CpiPr5)2 single-molecule magnet (SMM), which exhibits unusually long magnetization relaxation time, using the complete active space self-consistent field (CASSCF) method with spin–orbit interaction included within the restricted active space state interaction (RASSI). Our calculations show that the low-energy states arise from 4f8(6s,5dz2)1, 4f8(5dx2-y2)1, and 4f8(5dxy)1 configurations. We compute the hyperfine interaction parameters and the electronic–nuclear spectrum within our multiconfigurational approach. We find that the hyperfine interaction is about one order of magnitude greater than that for Tb(III)Pc2 SMMs. This stems from the strong Fermi contact interaction between the Tb nuclear spin and the electron spin density at the nucleus that originates from the occupation of the (6s,5d) orbitals. We also uncover that the response of the Fermi contact term to electric field results in electrical tuning of the electronic–nuclear level separations. This hyperfine Stark effect may be useful for applications of molecular nuclear spins for quantum computing.},
doi = {10.1039/d0cp04056h},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 38,
volume = 22,
place = {United States},
year = {Tue Sep 15 00:00:00 EDT 2020},
month = {Tue Sep 15 00:00:00 EDT 2020}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Lanthanide Double-Decker Complexes Functioning as Magnets at the Single-Molecular Level
journal, July 2003

  • Ishikawa, Naoto; Sugita, Miki; Ishikawa, Tadahiko
  • Journal of the American Chemical Society, Vol. 125, Issue 29
  • DOI: 10.1021/ja029629n

A silicon-based nuclear spin quantum computer
journal, May 1998


Expanding Rare-Earth Oxidation State Chemistry to Molecular Complexes of Holmium(II) and Erbium(II)
journal, May 2012

  • MacDonald, Matthew R.; Bates, Jefferson E.; Fieser, Megan E.
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja303357w

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980


Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment
journal, January 2017

  • Fieser, Megan E.; Palumbo, Chad T.; La Pierre, Henry S.
  • Chem. Sci., Vol. 8, Issue 11
  • DOI: 10.1039/C7SC02337E

Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe 3 ) 2 } 3 ] 1− Complexes of the Non-traditional +2 Lanthanide Ions
journal, May 2018

  • Ryan, Austin J.; Darago, Lucy E.; Balasubramani, Sree Ganesh
  • Chemistry - A European Journal, Vol. 24, Issue 30
  • DOI: 10.1002/chem.201800610

Molecular spins for quantum computation
journal, March 2019


The restricted active space (RAS) state interaction approach with spin–orbit coupling
journal, May 2002


A two-qubit molecular architecture for electron-mediated nuclear quantum simulation
journal, January 2018

  • Atzori, Matteo; Chiesa, Alessandro; Morra, Elena
  • Chemical Science, Vol. 9, Issue 29
  • DOI: 10.1039/C8SC01695J

Quantum computing in molecular magnets
journal, April 2001

  • Leuenberger, Michael N.; Loss, Daniel
  • Nature, Vol. 410, Issue 6830
  • DOI: 10.1038/35071024

Electrical Readout of Individual Nuclear Spin Trajectories in a Single-Molecule Magnet Spin Transistor
journal, July 2013


Quantum Tunneling of Magnetization in Lanthanide Single-Molecule Magnets: Bis(phthalocyaninato)terbium and Bis(phthalocyaninato)dysprosium Anions
journal, May 2005

  • Ishikawa, Naoto; Sugita, Miki; Wernsdorfer, Wolfgang
  • Angewandte Chemie International Edition, Vol. 44, Issue 19
  • DOI: 10.1002/anie.200462638

Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of Terbium(II) and Dysprosium(II)
journal, August 2019

  • Gould, Colin A.; McClain, K. Randall; Yu, Jason M.
  • Journal of the American Chemical Society, Vol. 141, Issue 33
  • DOI: 10.1021/jacs.9b05816

Synthetic Hilbert Space Engineering of Molecular Qu d its: Isotopologue Chemistry
journal, February 2019


Quantum technologies with optically interfaced solid-state spins
journal, August 2018


Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln 2+ Complexes and Unusual [Li(2.2.2-cryptand)] 1+ Cations
journal, February 2018


Quantum electrodynamical corrections to the fine structure of helium
journal, January 1974


Spin crossover iron(III) complexes
journal, November 2007


Magnetism in Ln molecular systems with 4f/valence-shell interplay (FV-magnetism)
journal, January 2019

  • Dubrovin, Vasilii; Popov, Alexey A.; Avdoshenko, Stanislav
  • Chemical Communications, Vol. 55, Issue 93
  • DOI: 10.1039/C9CC06913E

Electrically driven nuclear spin resonance in single-molecule magnets
journal, June 2014


Magnetic Anisotropy in Divalent Lanthanide Compounds
journal, May 2020

  • Zhang, Weibing; Muhtadi, Almas; Iwahara, Naoya
  • Angewandte Chemie International Edition, Vol. 59, Issue 31
  • DOI: 10.1002/anie.202003399

On the stability and bonding in bis(η-arene)ianthanide complexes
journal, January 1989

  • Anderson, David M.; Cloke, F. Geoffrey N.; Cox, P. Anthony
  • J. Chem. Soc., Chem. Commun., Issue 1
  • DOI: 10.1039/C39890000053

Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln 2+ Ions in the [K(2.2.2-cryptand)][(C 5 H 4 SiMe 3 ) 3 Ln] Complexes: The Variable Nature of Dy 2+ and Nd 2+
journal, December 2014

  • Fieser, Megan E.; MacDonald, Matthew R.; Krull, Brandon T.
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja510831n

Nature of Hyperfine Interactions in TbPc 2 Single-Molecule Magnets: Multiconfigurational Ab Initio Study
journal, February 2020


A mean-field spin-orbit method applicable to correlated wavefunctions
journal, March 1996


Enhancing coherence in molecular spin qubits via atomic clock transitions
journal, March 2016

  • Shiddiq, Muhandis; Komijani, Dorsa; Duan, Yan
  • Nature, Vol. 531, Issue 7594
  • DOI: 10.1038/nature16984

Observation of Cooperative Electronic Quantum Tunneling: Increasing Accessible Nuclear States in a Molecular Qudit
journal, April 2018


Structure:function relationships in molecular spin-crossover complexes
journal, January 2011


Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8
journal, November 2015

  • Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K.
  • Journal of Computational Chemistry, Vol. 37, Issue 5
  • DOI: 10.1002/jcc.24221

Lanthanide Single-Molecule Magnets
journal, March 2013

  • Woodruff, Daniel N.; Winpenny, Richard E. P.; Layfield, Richard A.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr400018q

Ab initio calculation of anisotropic magnetic properties of complexes. I. Unique definition of pseudospin Hamiltonians and their derivation
journal, August 2012

  • Chibotaru, L. F.; Ungur, L.
  • The Journal of Chemical Physics, Vol. 137, Issue 6
  • DOI: 10.1063/1.4739763

Effects from Spin–Orbit Coupling on Electron–Nucleus Hyperfine Coupling Calculated at the Restricted Active Space Level for Kramers Doublets
journal, January 2015

  • Sharkas, Kamal; Pritchard, Ben; Autschbach, Jochen
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 2
  • DOI: 10.1021/ct500988h

Luscus: molecular viewer and editor for MOLCAS
journal, April 2015


Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr 2+ , Gd 2+ , Tb 2+ , and Lu 2+
journal, May 2013

  • MacDonald, Matthew R.; Bates, Jefferson E.; Ziller, Joseph W.
  • Journal of the American Chemical Society, Vol. 135, Issue 26
  • DOI: 10.1021/ja403753j

Record High Single-Ion Magnetic Moments Through 4f n 5d 1 Electron Configurations in the Divalent Lanthanide Complexes [(C 5 H 4 SiMe 3 ) 3 Ln]
journal, July 2015

  • Meihaus, Katie R.; Fieser, Megan E.; Corbey, Jordan F.
  • Journal of the American Chemical Society, Vol. 137, Issue 31
  • DOI: 10.1021/jacs.5b03710

The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule
journal, February 1981

  • Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders
  • The Journal of Chemical Physics, Vol. 74, Issue 4
  • DOI: 10.1063/1.441359

Operating Quantum States in Single Magnetic Molecules: Implementation of Grover’s Quantum Algorithm
journal, November 2017