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Nature of Hyperfine Interactions in TbPc2 Single-Molecule Magnets: Multiconfigurational Ab Initio Study

Journal Article · · Inorganic Chemistry
 [1];  [2]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Virginia Tech
  2. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
+ Show Author Affiliations
Lanthanide-based single-ion magnetic molecules can have large magnetic hyperfine interactions as well as large magnetic anisotropy. Recent experimental studies reported tunability of these properties by changes of chemical environments or by application of external stimuli for device applications. In order to provide insight onto the origin and mechanism of such tunability, here we investigate the magnetic hyperfine and nuclear quadrupole interactions for a 159Tb nucleus in TbPc2 (Pc = phthalocyanine) single-molecule magnets using multiconfigurational ab initio methods including spin–orbit interaction. Since the electronic ground and first-excited (quasi)doublets are well separated in energy, the microscopic Hamiltonian can be mapped onto an effective Hamiltonian with an electronic pseudospin S = 1/2. From the ab initio calculated parameters, we find that the magnetic hyperfine coupling is dominated by the interaction of the Tb nuclear spin with electronic orbital angular momentum. The asymmetric 4f-like electronic charge distribution leads to a strong nuclear quadrupole interaction with significant transverse terms for the molecule with low symmetry. The ab initio calculated electronic–nuclear spectrum including the magnetic hyperfine and quadrupole interactions is in excellent agreement with the experiment. We further find that the transverse quadrupole interactions significantly influence the avoided level crossings in magnetization dynamics and that the molecular distortions affect mostly the Fermi contact terms as well as the transverse quadrupole interactions.

Synopsis

Hyperfine interactions for 159Tb nucleus in TbPc2 single-molecule magnets are investigated from first-principles using multiconfigurational calculations. Strong nuclear quadrupole and magnetic hyperfine coupling are found, with the latter being dominated by the paramagnetic spin-orbital mechanism. Furthermore, we construct an ab initio pseudospin Hamiltonian and obtain the electronic-nuclear spectrum that is in excellent agreement with experiment. The Zeeman diagram is calculated, and the magnetization dynamics is discussed. The effects of molecular distortions are researched.

Research Organization:
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Organization:
San Diego Supercomputer Center (SDSC)
Grant/Contract Number:
SC0018326
OSTI ID:
1631159
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 59; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY