Skip to content
6CCVD Research

Simulation of Indirect 13C–13C J-Coupling Tensors in Diamond Clusters Hosting the NV Center

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2022-04-22
AuthorsAlexander Nizovtsev, Aliaksandr Pushkarchuk, S. A. Kuten, Dominik L. Michels, Dmitry Lyakhov
InstitutionsNational Research Nuclear University MEPhI, Institute of Physical and Organic Chemistry
Citations1
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”

This study presents the first quantum-chemical simulation of the full indirect 13C-13C J-coupling tensors (JKL) in H-terminated diamond clusters, including those hosting a negatively charged Nitrogen-Vacancy (NV-) center.

  • Core Achievement: Successful simulation of the full J-coupling tensor (JKL) for 13C nuclear spins in diamond clusters, moving beyond the traditionally measured isotropic scalar constant (Jiso).
  • Validation: Calculated isotropic J-coupling constants (1Jiso) for nearest-neighbor (N-N) 13C-13C pairs in bulk-like clusters (C35H36) were 29.8-30.0 Hz, closely matching the experimental value of 31.4 ± 0.5 Hz.
  • NV Center Impact: The presence of the NV- center significantly affects J-coupling characteristics, particularly for 13C pairs located near the vacancy.
  • Quantified NV Effect: For 13C pairs nearest to the NV vacancy, the isotropic J-coupling constant (1Jiso) increased substantially, reaching up to ~37.1 Hz (a relative increase of approximately 9%).
  • Anisotropy Confirmation: The simulations confirm that anisotropic contributions to the J-coupling tensor are essential in crystalline solids and must be accounted for, as they are not averaged out as in solution-state NMR.
  • Application Relevance: The data provides critical high-resolution NMR parameters necessary for designing and optimizing NV-based quantum memory devices and nanoscale magnetic sensors.

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
Isotropic J-Coupling (Simulated, Bulk)29.8 - 30.0HzNearest-neighbor (N-N) 13C-13C pairs in C35H36 cluster.
Isotropic J-Coupling (Experimental)31.4 ± 0.5HzN-N 13C-13C pairs in bulk diamond.
Isotropic J-Coupling (NV Proximity)~37.1HzN-N 13C-13C pairs nearest to the NV- vacancy (C33[NV-]H36).
J-Coupling Increase due to NV~9%Relative increase in 1Jiso for pairs near the vacancy.
Asymmetric Part (A1J)-11.74HzCalculated for the C1-C2 pair in adamantane (transformed coordinate system).
Cluster Size (Adamantane)C10H16AtomsTest molecule for method validation.
Cluster Size (NV Host)C33[NV-]H36AtomsCluster hosting the negatively charged NV- center.
N-N 13C-13C Bond Length~1.54AngstromStandard single C-C bond length in diamond.

Key Methodologies

Section titled “Key Methodologies”

The indirect 13C-13C J-coupling tensors were simulated using Density Functional Theory (DFT) on H-terminated diamond clusters.

  1. Software Platform: Calculations were performed using the ORCA package (version 5.0.2).
  2. Cluster Modeling: Diamond was modeled using H-terminated carbon clusters: Adamantane (C10H16), a larger bulk-like cluster (C35H36), and the NV-hosting cluster (C33[NV-]H36).
  3. Geometry Optimization: Cluster geometries were optimized using the B3LYP/def2/J/RIJCOSX level of theory.
  4. J-Coupling Calculation Level: The n-bond J-coupling tensors (JKL) were simulated using the B3LYP/TZVPP/AUTOAUX/decontract level of theory.
  5. Basis Set Selection: The TZVPP basis set, combined with the B3LYP functional, was specifically chosen as recommended for accurate NMR calculations.
  6. Interaction Components: The simulation calculated all contributions to the total JKL tensor, including:
    • Diamagnetic
    • Paramagnetic
    • Fermi-contact (main contribution)
    • Spin-dipolar
    • Spin-dipolar/Fermi contact cross-term
  7. Computational Resources: All computations were executed on KAUST’s Ibex High-Performance Computing (HPC) cluster.

Commercial Applications

Section titled “Commercial Applications”

The accurate prediction of J-coupling tensors is foundational for technologies relying on precise nuclear spin control and sensing in solid-state diamond systems.

  • Quantum Computing and Memory: Essential for the creation and control of long-lived quantum memory based on singlet-state 13C-13C dimers in diamond, which are coupled to the NV center electron spin.
  • Nanoscale Magnetic Sensing: Enables the development of high-resolution NV-based magnetometers capable of detecting and characterizing target single 13C nuclear spins or coupled 13C-13C pairs.
  • Chemical Analysis (Single-Spin NMR): Allows for the determination of molecular structures of inorganic or biological compounds adsorbed onto nanostructured diamond surfaces by distinguishing inequivalent nuclear spins via chemical shifts and J-coupling.
  • Biomedical Technology: Supports applications in targeted drug delivery, monitoring biological processes at the individual cell level, and advanced medical imaging.
  • Ultralow-Field NMR: Provides necessary data for modeling and studying NMR spectra in the zero- to ultralow-field regime, where internal spin interactions dominate.
View Original Abstract

The full tensors nJKL (K,L = X,Y,Z), describing n-bond J-coupling of nuclear spins 13C in H-terminated diamond-like clusters C10H16 (adamantane) and C35H36, as well as in the cluster C33[NV−]H36 hosting the negatively charged NV−center, were simulated. We found that, in addition to the usually considered isotropic scalar nJ-coupling constant, the anisotropic contributions to the nJ-coupling tensor are essential. We also showed that the presence of the NV center affects the J-coupling characteristics, especially in the case of 13C–13C pairs located near the vacancy of the NV center.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2019 - Blueprint for nanoscale NMR [Crossref]
  2. 2020 - Sensitivity optimization for NV-diamond magnetometry [Crossref]
  3. 2017 - Steady-state preparation of long-lived nuclear spin singlet pairs at room temperature [Crossref]
  4. 2018 - High-resolution magnetic resonance spectroscopy using a solid-state spin sensor
  5. 2009 - NMR line shapes from AB spin systems in solids—The role of antisymmetric spin-spin coupling [Crossref]
  6. 2001 - Spin-1/2 and beyond: A perspective in solid state NMR spectroscopy [Crossref]
  7. 2021 - Solid-state NMR spectroscopy [Crossref]
  8. 2002 - Spin-spin coupling tensors as determined by experiment and computational chemistry [Crossref]
  9. 2017 - NMR lineshape of 29Si in single-crystal silicon [Crossref]
  10. 1994 - NMR spectra of pure 13C diamond [Crossref]

Reads Similar to This

Shaped Pulses for Energy-Efficient High-Field NMR at the Nanoscale Nanostructuring of Dysprosocenium Single-Ion Magnets through Encapsulation in MOFs - A Promising Approach to Achieve High Axiality and Ambient Stability with Long-Range Ordering Pushing the limits of microfocus X-ray sealed-tube sources for crystallography