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Register a new userRapid and Precise Determination of Zero-Field Splittings by Terahertz Time-Domain Electron Paramagnetic Resonance Spectroscopy
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Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science.
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Electron paramagnetic resonance spectroscopy (EPR) is among the most important analytical tools in physics, chemistry, and biology. The emergence of nitrogen-vacancy (NV) centers in diamond, serving as an atomic-sized magnetometer, has promoted this technique to single-spin level, even under ambient conditions. Despite the enormous progress in spatial resolution, the current megahertz spectral resolution is still insufficient to resolve key heterogeneous molecular information. A major challenge is the short coherence times of the sample electron spins. Here, we address this challenge by employing a magnetic noise-insensitive transition between states of different symmetry. We demonstrate a 27-fold narrower spectrum of single substitutional nitrogen (P1) centers in diamond with linewidth of several kilohertz, and then some weak couplings can be resolved. Those results show both spatial and spectral advances of NV center-based EPR, and provide a route towards analytical (EPR) spectroscopy at single-molecule level.
Electron spin resonance (ESR) spectroscopy has broad applications in physics, chemistry and biology. As a complementary tool, zero-field ESR (ZF-ESR) spectroscopy has been proposed for decades and shown its own benefits for investigating the electron fine and hyperfine interaction. However, the ZF-ESR method has been rarely used due to the low sensitivity and the requirement of much larger samples than conventional ESR. In this work, we present a method for deploying ZF-ESR spectroscopy at the nanoscale by using a highly sensitive quantum sensor, the nitrogen-vacancy center in diamond. We also measure the nanoscale ZF-ESR spectrum of a few P1 centers in diamond, and show that the hyperfine coupling constant can be directly extracted from the spectrum. This method opens the door to practical applications of ZF-ESR spectroscopy, such as investigation of the structure and polarity information in spin-modified organic and biological systems.
We present single- and multiple-quantum correlation $J$-spectroscopy detected in zero ($<!!1$~$mu$G) magnetic field using a Rb vapor-cell magnetometer. At zero field the spectrum of ethanol appears as a mixture of carbon isotopomers, and correlation spectroscopy is useful in separating the two composite spectra. We also identify and observe the zero-field equivalent of a double-quantum transition in ${}^{13}$C$_2$-acetic acid, and show that such transitions are of use in spectral assignment. Two-dimensional spectroscopy further improves the high resolution attained in zero-field NMR since selection rules on the coherence-transfer pathways allow for the separation of otherwise overlapping resonances into distinct cross-peaks.
Electron paramagnetic resonance (EPR) spectroscopy is an important technology in physics, chemistry, materials science, and biology. Sensitive detection with a small sample volume is a key objective in these areas, because it is crucial, for example, for the readout of a highly packed spin based quantum memory or the detection of unlabeled metalloproteins in a single cell. In conventional EPR spectrometers, the energy transfer from the spins to the cavity at a Purcell enhanced rate plays an essential role and requires the spins to be resonant with the cavity, however the size of the cavity (limited by the wavelength) makes it difficult to improve the spatial resolution. Here, we demonstrate a novel EPR spectrometer using a single artificial atom as a sensitive detector of spin magnetization. The artificial atom, a superconducting flux qubit, provides advantages both in terms of its quantum properties and its much stronger coupling with magnetic fields. We have achieved a sensitivity of $sim$400 spins/$sqrt{mathrm{Hz}}$ with a magnetic sensing volume around $10^{-14} lambda^3$ (50 femto-liters). This corresponds to an improvement of two-order of magnitude in the magnetic sensing volume compared with the best cavity based spectrometers while maintaining a similar sensitivity as those spectrometers . Our artificial atom is suitable for scaling down and thus paves the way for measuring single spins on the nanometer scale.
Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) is an alternative spectroscopic method to high-field NMR, in which samples are studied in the absence of a large magnetic field. Unfortunately, there is a large barrier to entry for many groups, because operating the optical magnetometers needed for signal detection requires some expertise in atomic physics and optics. Commercially available magnetometers offer a solution to this problem. Here we describe a simple ZULF NMR configuration employing commercial magnetometers, and demonstrate sufficient functionality to measure samples with nuclear spins prepolarized in a permanent magnet or initialized using parahydrogen. This opens the possibility for other groups to use ZULF NMR, which provides a means to study complex materials without magnetic susceptibility-induced line broadening, and to observe samples through conductive materials.
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