Hyperfine and quadrupole interactions for Dy isotopes in DyPc<sub>2</sub> molecules

Wysocki, Aleksander L.; Park, Kyungwha

doi:10.1088/1361-648x/ab757b

Cited by 6 publications

(8 citation statements)

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“…CeCl 6 3– has a simple electronic structure, and prior calculations are available for comparison. Finally, the TbPc 2 complex (Figure shown later) and its anion were chosen because the system has attracted attention recently in the context of single-molecule magnetism, and calculated HFC data were reported for the system, obtained with nonrelativistic hyperfine operators in an SO–RASSI approach that was essentially equivalent to the one of ref . Because of the large size of the ligand, truncated models for TbPc 2 were set up by removing peripheral atoms from the available crystal structures and capping dangling bonds by hydrogen atoms whose positions were optimized with DFT.…”

Section: Resultsmentioning

confidence: 99%

“…As an example for the latter, it was shown that the calculated HFC of 237 Np in NpF 6 agreed very well with experimental data. The same approach, effectively, was also used by others recently to calculate the HFC parameters of Tb and Dy in lanthanide complexes. , …”

Section: Introductionmentioning

confidence: 99%

“…The same approach, effectively, was also used by others recently to calculate the HFC parameters of Tb and Dy in lanthanide complexes. 71,72 The present article is concerned with the generalization of the HFC approach reported in ref 19 to X2C, based on the X2C-transformed nuclear magnetic hyperfine operator as described in ref 53. The implementation was carried out in OpenMolcas.…”

Section: Introductionmentioning

confidence: 99%

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Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Feng

Duignan

Autschbach

2021

J. Chem. Theory Comput.

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Exact two-component (X2C) relativistic nuclear hyperfine magnetic field operators were incorporated in X2C ab initio wavefunction calculations at the multireference restricted active space (RAS) level for calculations of nuclear hyperfine magnetic properties. Spin–orbit coupling was treated via RAS state interaction (SO–RASSI). The method was tested by calculations of electron–nucleus hyperfine coupling constants. The approach, implemented in the OpenMolcas program, overcomes a major limitation of a previous SO–RASSI implementation for hyperfine coupling that relied on nonrelativistic hyperfine operators [J. Chem. Theor. Comput. 2015, 11, 538–549] and therefore had limited applicability. Results from calculations on systems with light and heavy main group elements, transition metals, lanthanides, and one actinide complex demonstrate reasonably good agreement with experimental data, where available, as long as the active space can generate sufficient spin polarization.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Feng

Duignan

Autschbach

2021

J. Chem. Theory Comput.

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“…As an example, in a neutral Tb(II)(CpiPr 5 ) 2 single-molecule magnet (SMM), the hyperfine interaction of the 159 Tb nucleus is approximately 1 order of magnitude greater than that observed in Tb(III)Pc 2 SMMs . Moreover, the hyperfine constant of 163 Dy(II) is measured to be 162.6 MHz, which is greater than that of 163 Dy(III), recorded as 152.4 MHz. − Consequently, reducing 163 Dy(III) to 163 Dy(II) has the potential to further increase the level of the hyperfine interaction.…”

Section: Resultsmentioning

confidence: 96%

Hilbert Space in Isotopologue Dy(III) SMM Dimers: Dipole Interaction Limit in [^163/164Dy₂(tmhd)₆(tape)]⁰ Complexes

Ruan,

Moreno-Pineda,

Schulze

et al. 2023

Inorg. Chem.

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Single-molecule magnets are molecular complexes proposed to be useful for information storage and quantum information processing applications. In the quest for multilevel systems that can act as Qudits, two dysprosium-based isotopologues were synthesized and characterized. The isotopologues are [ 164 Dy 2 (tmhd) 6 (tape)] (1 (I=0) ) and [ 163 Dy 2 (tmhd) 6 (tape)] (2 (I=5/2) ), where tmhd = 2,2,6,6-tetramethylheptandionate and tape = 1,6,7,12-tetraazaperylene. Both complexes showed slow relaxation at a zero applied magnetic field with dominant Orbach and Raman relaxation mechanisms. μSQUID studies at milli-Kelvin temperatures reveal quasi-single ion loops, in contrast with the expected S-shape (near zero field) butterfly loops, characteristic of antiferromagnetically coupled dimeric complexes. Through analysis of the low-temperature data, we find that the interaction operating between Dy(III) is small, leading to a small exchange biasing from the zero-field transition. The resulting indirectly coupled nuclear states are degenerate or possess a small energy difference between them. We, therefore, conclude that for the creation of Qudits with enlarged Hilbert spaces, shorter Dy(III)•••Dy(III) distances are deemed essential.

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“…MHz due to presence of small but nonzero A xx and A yy parameters40 ). The levels can be characterized by zprojections of the electronic pseudospin (m S =↑, ↓) and the nuclear spin (M I = ±3/2, ±1/2).…”

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confidence: 99%

Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp$^{\rm{iPr5}}$)$_2$ single-molecule magnet

Smith,

Wysocki,

Park

2020

Preprint

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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 Ln 2+ have a strong interaction between the Ln nuclear spin and the electronic degrees of freedom, which renders electrical tuning of the interaction.As an example, we study electronic structure and hyperfine interaction of the 159 Tb nucleus in a neutral Tb(II)(Cp iPr5 ) 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 4 f 8 (6s, 5d z 2 ) 1 , 4 f 8 (5d x 2 −y 2 ) 1 , and 4 f 8 (5d xy ) 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)Pc 2 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.

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Hyperfine and quadrupole interactions for Dy isotopes in DyPc₂ molecules

Cited by 6 publications

References 48 publications

Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Hilbert Space in Isotopologue Dy(III) SMM Dimers: Dipole Interaction Limit in [^163/164Dy₂(tmhd)₆(tape)]⁰ Complexes

Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp$^{\rm{iPr5}}$)$_2$ single-molecule magnet

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Hyperfine and quadrupole interactions for Dy isotopes in DyPc2 molecules

Cited by 6 publications

References 48 publications

Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Hilbert Space in Isotopologue Dy(III) SMM Dimers: Dipole Interaction Limit in [163/164Dy2(tmhd)6(tape)]0 Complexes

Electrically tuned hyperfine spectrum in neutral Tb(II)(Cp$^{\rm{iPr5}}$)$_2$ single-molecule magnet

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Hyperfine and quadrupole interactions for Dy isotopes in DyPc₂ molecules

Hilbert Space in Isotopologue Dy(III) SMM Dimers: Dipole Interaction Limit in [^163/164Dy₂(tmhd)₆(tape)]⁰ Complexes