In physics, optically detected magnetic resonance (ODMR) is a double resonance technique by which the electron spin state of a crystal defect may be optically pumped for spin initialisation and readout. [1]
Like electron paramagnetic resonance (EPR), ODMR makes use of the Zeeman effect in unpaired electrons. The negatively charged nitrogen vacancy centre (NV−) has been the target of considerable interest with regards to performing experiments using ODMR. [2]
ODMR of NV−s in diamond has applications in magnetometry [3] and sensing, biomedical imaging, quantum information and the exploration of fundamental physics.
The nitrogen vacancy defect in diamond consists of a single substitutional nitrogen atom (replacing one carbon atom) and an adjacent gap, or vacancy, in the lattice where normally a carbon atom would be located.
The nitrogen vacancy occurs in three possible charge states: positive (NV+), neutral (NV0) and negative (NV−). [4] As NV− is the only one of these charge states which has shown to be ODMR active, it is often referred to simply as the NV.
The energy level structure of the NV− consists of a triplet ground state, a triplet excited state and two singlet states. Under resonant optical excitation, the NV may be raised from the triplet ground state to the triplet excited state. The centre may then return to the ground state via two routes; by the emission of a photon of 637 nm in the zero phonon line (ZPL) (or longer wavelength from the phonon sideband) or alternatively via the aforementioned singlet states through intersystem crossing and the emission of a 1042 nm photon. A return to the ground state via the latter route will preferentially result in the state.
Relaxation to the state necessarily results in a decrease in visible wavelength fluorescence (as the emitted photon is in the infrared range). Microwave pumping at a resonant frequency of places the centre in the degenerate state. The application of a magnetic field lifts this degeneracy, causing Zeeman splitting and the decrease of fluorescence at two resonant frequencies, given by , where is the Planck constant, is the electron g-factor and is the Bohr magneton. Sweeping the microwave field through these frequencies results in two characteristic dips in the observed fluorescence, the separation between which enables determination of the strength of the magnetic field .
Further splitting in the fluorescence spectrum may occur due to the hyperfine interaction, which leads to further resonance conditions and corresponding spectral lines. In NV ODMR, this detailed structure usually originates from nitrogen and carbon-13 atoms near to the defect. These atoms have small magnetic fields which interact with the spectral lines from the NV, causing further splitting.
Hyperfine interactions in nitrogen-vacancy (NV) centres arise from nearby nuclear spins, primarily due to nitrogen (14N or 15N) and, in some cases 13C atoms near the defect. These interactions are significant because they further split the energy levels of the NV center, resulting in additional resonances in the ODMR spectrum. The nitrogen atom in the NV centre can exist as either 14N (with nuclear spin I = 1) or 15N (with nuclear spin I=1/2). The most common isotope, 14N, couples with the electron spin of the NV center, leading to a hyperfine splitting of the states into three sub-levels.
The interaction of NV electron spin with 14N nuclear spin can be defined by the hamiltonian shown above where S represents NV electron spin system and I represents nitrogen nuclear spin. This splitting typically depends upon the constants MHz and MHz. Splitting can be observed as three peaks in the ODMR hyperfine resolved spectrum. In NV centres, hyperfine splitting arises due to the interaction between the NV electron spin magnetic spin moment and nuclear spin magnetic moments. NV spin magnetic moments also depend upon the external magnetic field magnitude and orientation [5] . To perform hyperfine resolved ODMR, a single NV ODMR experiment is generally preferable. If 15N is present instead of 14N. It will split into two sublevels. [6]
Nearby 13C atoms (with nuclear spin I=1/2) can also interact with the NV centre (3). 13C carbon atoms are randomly distributed in diamonds and have a natural abundance of about 1.1%. When located near the NV center, they induce additional fine structures in the ODMR signal. The coupling strength varies with the position of the 13C nuclei relative to the NV center. [7]
The Zeeman effect is the effect of splitting of a spectral line into several components in the presence of a static magnetic field. It is named after the Dutch physicist Pieter Zeeman, who discovered it in 1896 and received a Nobel prize for this discovery. It is analogous to the Stark effect, the splitting of a spectral line into several components in the presence of an electric field. Also similar to the Stark effect, transitions between different components have, in general, different intensities, with some being entirely forbidden, as governed by the selection rules.
In atomic physics, hyperfine structure is defined by small shifts in otherwise degenerate electronic energy levels and the resulting splittings in those electronic energy levels of atoms, molecules, and ions, due to electromagnetic multipole interaction between the nucleus and electron clouds.
In physics and chemistry, the spin quantum number is a quantum number that describes the intrinsic angular momentum of an electron or other particle. It has the same value for all particles of the same type, such as s = 1/2 for all electrons. It is an integer for all bosons, such as photons, and a half-odd-integer for all fermions, such as electrons and protons.
Dynamic nuclear polarization (DNP) is one of several hyperpolarization methods developed to enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy. While an essential analytical tool with applications in several fields, NMR’s low sensitivity poses major limitations to analyzing samples with low concentrations and limited masses and volumes. This low sensitivity is due to the relatively low nuclear gyromagnetic ratios (γn) of NMR active nuclei (1H, 13C, 15N, etc.) as well as the low natural abundance of certain nuclei. Several techniques have been developed to address this limitation, including hardware adjustments to NMR instruments and equipment (e.g., NMR tubes), improvements to data processing methods, and polarization transfer methods to NMR active nuclei in a sample—under which DNP falls.
In the physical theory of spin glass magnetization, the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction models the coupling of nuclear magnetic moments or localized inner d- or f-shell electron spins through conduction electrons. It is named after Malvin Ruderman, Charles Kittel, Tadao Kasuya, and Kei Yosida, the physicists who first proposed and developed the model.
In atomic physics, the electron magnetic moment, or more specifically the electron magnetic dipole moment, is the magnetic moment of an electron resulting from its intrinsic properties of spin and electric charge. The value of the electron magnetic moment is −9.2847646917(29)×10−24 J⋅T−1. In units of the Bohr magneton (μB), it is −1.00115965218059(13) μB, a value that was measured with a relative accuracy of 1.3×10−13.
In quantum mechanics, the spin–orbit interaction is a relativistic interaction of a particle's spin with its motion inside a potential. A key example of this phenomenon is the spin–orbit interaction leading to shifts in an electron's atomic energy levels, due to electromagnetic interaction between the electron's magnetic dipole, its orbital motion, and the electrostatic field of the positively charged nucleus. This phenomenon is detectable as a splitting of spectral lines, which can be thought of as a Zeeman effect product of two effects: the apparent magnetic field seen from the electron perspective due to special relativity and the magnetic moment of the electron associated with its intrinsic spin due to quantum mechanics.
Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique based on re-orientation of atomic nuclei with non-zero nuclear spins in an external magnetic field. This re-orientation occurs with absorption of electromagnetic radiation in the radio frequency region from roughly 4 to 900 MHz, which depends on the isotopic nature of the nucleus and increased proportionally to the strength of the external magnetic field. Notably, the resonance frequency of each NMR-active nucleus depends on its chemical environment. As a result, NMR spectra provide information about individual functional groups present in the sample, as well as about connections between nearby nuclei in the same molecule. As the NMR spectra are unique or highly characteristic to individual compounds and functional groups, NMR spectroscopy is one of the most important methods to identify molecular structures, particularly of organic compounds.
Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spins excited are those of the electrons instead of the atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes and organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford.
Imperfections in the crystal lattice of diamond are common. Such defects may be the result of lattice irregularities or extrinsic substitutional or interstitial impurities, introduced during or after the diamond growth. The defects affect the material properties of diamond and determine to which type a diamond is assigned; the most dramatic effects are on the diamond color and electrical conductivity, as explained by the electronic band structure.
Proton nuclear magnetic resonance is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the structure of its molecules. In samples where natural hydrogen (H) is used, practically all the hydrogen consists of the isotope 1H.
Spin chemistry is a sub-field of chemistry positioned at the intersection of chemical kinetics, photochemistry, magnetic resonance and free radical chemistry, that deals with magnetic and spin effects in chemical reactions. Spin chemistry concerns phenomena such as chemically induced dynamic nuclear polarization (CIDNP), chemically induced electron polarization (CIDEP), magnetic isotope effects in chemical reactions, and it is hypothesized to be key in the underlying mechanism for avian magnetoreception and consciousness.
In nuclear chemistry and nuclear physics, J-couplings are mediated through chemical bonds connecting two spins. It is an indirect interaction between two nuclear spins that arises from hyperfine interactions between the nuclei and local electrons. In NMR spectroscopy, J-coupling contains information about relative bond distances and angles. Most importantly, J-coupling provides information on the connectivity of chemical bonds. It is responsible for the often complex splitting of resonance lines in the NMR spectra of fairly simple molecules.
Zero field splitting (ZFS) describes various interactions of the energy levels of a molecule or ion resulting from the presence of more than one unpaired electron. In quantum mechanics, an energy level is called degenerate if it corresponds to two or more different measurable states of a quantum system. In the presence of a magnetic field, the Zeeman effect is well known to split degenerate states. In quantum mechanics terminology, the degeneracy is said to be "lifted" by the presence of the magnetic field. In the presence of more than one unpaired electron, the electrons mutually interact to give rise to two or more energy states. Zero field splitting refers to this lifting of degeneracy even in the absence of a magnetic field. ZFS is responsible for many effects related to the magnetic properties of materials, as manifested in their electron spin resonance spectra and magnetism.
The nitrogen-vacancy center is one of numerous photoluminescent point defects in diamond. Its most explored and useful properties include its spin-dependent photoluminescence, and its relatively long (millisecond) spin coherence at room temperature. The NV center energy levels are modified by magnetic fields, electric fields, temperature, and strain, which allow it to serve as a sensor of a variety of physical phenomena. Its atomic size and spin properties can form the basis for useful quantum sensors. It has also been explored for applications in quantum computing, quantum simulation, and spintronics.
Electron nuclear double resonance (ENDOR) is a magnetic resonance technique for elucidating the molecular and electronic structure of paramagnetic species. The technique was first introduced to resolve interactions in electron paramagnetic resonance (EPR) spectra. It is currently practiced in a variety of modalities, mainly in the areas of biophysics and heterogeneous catalysis.
Magnetochemistry is concerned with the magnetic properties of chemical compounds and elements. Magnetic properties arise from the spin and orbital angular momentum of the electrons contained in a compound. Compounds are diamagnetic when they contain no unpaired electrons. Molecular compounds that contain one or more unpaired electrons are paramagnetic. The magnitude of the paramagnetism is expressed as an effective magnetic moment, μeff. For first-row transition metals the magnitude of μeff is, to a first approximation, a simple function of the number of unpaired electrons, the spin-only formula. In general, spin–orbit coupling causes μeff to deviate from the spin-only formula. For the heavier transition metals, lanthanides and actinides, spin–orbit coupling cannot be ignored. Exchange interaction can occur in clusters and infinite lattices, resulting in ferromagnetism, antiferromagnetism or ferrimagnetism depending on the relative orientations of the individual spins.
Nitrogen-15 nuclear magnetic resonance spectroscopy is a version of nuclear magnetic resonance spectroscopy that examines samples containing the 15N nucleus. 15N NMR differs in several ways from the more common 13C and 1H NMR. To circumvent the difficulties associated with measurement of the quadrupolar, spin-1 14N nuclide, 15N NMR is employed in samples for detection since it has a ground-state spin of ½. Since14N is 99.64% abundant, incorporation of 15N into samples often requires novel synthetic techniques.
Electric dipole spin resonance (EDSR) is a method to control the magnetic moments inside a material using quantum mechanical effects like the spin–orbit interaction. Mainly, EDSR allows to flip the orientation of the magnetic moments through the use of electromagnetic radiation at resonant frequencies. EDSR was first proposed by Emmanuel Rashba.
The T centre is a radiation damage centre in silicon composed of a carbon-carbon pair (C-C) sharing a substitutional site of the silicon lattice. Additionally, one of the substitutional carbon atoms is bonded with a hydrogen atom while the other carbon contains an unpaired electron in the ground state of a dangling bond. Much like the nitrogen-vacancy centres in diamond, the T centre contains spin-dependent optical transitions addressable through photoluminescence. These spin-dependent transitions, however, emit light within the technologically efficient telecommunication O-band. Consequentially, the T centre is an intriguing candidate for quantum information technologies with development of integrated quantum devices benefiting from techniques within the silicon photonic community.
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