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John W. Blanchard

Publications and source records attributed to John W. Blanchard.

44 records · Page 3Linked to original sources

Measuring molecular parity nonconservation using nuclear magnetic resonance spectroscopy

The weak interaction does not conserve parity and therefore induces energy shifts in chiral enantiomers that should in principle be detectable in molecular spectra. Unfortunately, the magnitude of the expected shifts are small and in spectra of a mixture of enantiomers, the energy shifts are not resolvable. We propose a nuclear magnetic resonance (NMR) experiment in which we titrate the chirality (enantiomeric excess) of a solvent and measure the diasteriomeric splitting in the spectra of a chiral solute in order to search for an anomalous offset due to parity nonconservation (PNC). We present a proof-of-principle experiment in which we search for PNC in the \textsuperscript{13}C resonances of small molecules, and use the \textsuperscript{1}H resonances, which are insensitive to PNC, as an internal reference. We set a new constraint on molecular PNC in \textsuperscript{13}C chemical shifts at a level of $10^{-5}$\,ppm, and provide a discussion of important considerations in the search for molecular PNC using NMR spectroscopy.

physics.chem-ph↗

Experimental Benchmarking of Quantum Control in Zero-Field Nuclear Magnetic Resonance

Zero-field nuclear magnetic resonance (NMR) provides complementary analysis modalities to those of high-field NMR and allows for ultra-high-resolution spectroscopy and measurement of untruncated spin-spin interactions. Unlike for the high-field case, however, universal quantum control -- the ability to perform arbitrary unitary operations -- has not been experimentally demonstrated in zero-field NMR. This is because the Larmor frequency for all spins is identically zero at zero field, making it challenging to individually address different spin species. We realize a composite-pulse technique for arbitrary independent rotations of $^1$H and $^{13}$C spins in a two-spin system. Quantum-information-inspired randomized benchmarking and state tomography are used to evaluate the quality of the control. We experimentally demonstrate single-spin control for $^{13}$C with an average gate fidelity of $0.9960(2)$ and two-spin control via a controlled-not (CNOT) gate with an estimated fidelity of $0.99$. The combination of arbitrary single-spin gates and a CNOT gate is sufficient for universal quantum control of the nuclear spin system. The realization of complete spin control in zero-field NMR is an essential step towards applications to quantum simulation, entangled-state-assisted quantum metrology, and zero-field NMR spectroscopy.

quant-ph↗

Instrumentation for nuclear magnetic resonance in zero and ultralow magnetic field

We review instrumentation for nuclear magnetic resonance (NMR) in zero and ultra-low magnetic field (ZULF, below 0.1 $μ$T) where detection is based on a low-cost, non-cryogenic, spin-exchange relaxation free (SERF) $^{87}$Rb atomic magnetometer. The typical sensitivity is 20-30 fT/Hz$^{1/2}$ for signal frequencies below 1 kHz and NMR linewidths range from Hz all the way down to tens of mHz. These features enable precision measurements of chemically informative nuclear spin-spin couplings as well as nuclear spin precession in ultra-low magnetic fields.

physics.ins-det↗

A Method for Measurement of Spin-Spin Couplings with sub-mHz Precision Using Zero- to Ultralow-Field Nuclear Magnetic Resonance

We present a method which allows for the extraction of physical quantities directly from zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) data. A numerical density matrix evolution is used to simulate ZULF NMR spectra of several molecules in order to fit experimental data. The method is utilized to determine the indirect spin-spin couplings ($J$-couplings) in these, which is achieved with precision of $10^{-2}$--$10^{-4}$ Hz. The simulated and measured spectra are compared to earlier research. Agreement and precision improvement for most of the $J$-coupling estimates are achieved. The availability of an efficient, flexible fitting method for ZULF NMR enables a new generation of precision-measurement experiments for spin-dependent interactions and physics beyond the Standard Model.

physics.chem-ph↗

Antisymmetric Couplings Enable Direct Observation of Chirality in Nuclear Magnetic Resonance Spectroscopy

Here we demonstrate that a term in the nuclear spin Hamiltonian, the antisymmetric \textit{J}-coupling, is fundamentally connected to molecular chirality. We propose and simulate a nuclear magnetic resonance (NMR) experiment to observe this interaction and differentiate between enantiomers without adding any additional chiral agent to the sample. The antisymmetric \textit{J}-coupling may be observed in the presence of molecular orientation by an external electric field. The opposite parity of the antisymmetric coupling tensor and the molecular electric dipole moment yields a sign change of the observed coupling between enantiomers. We show how this sign change influences the phase of the NMR spectrum and may be used to discriminate between enantiomers.

quant-ph↗

Eddy current imaging with an atomic radio-frequency magnetometer

We use a radio-frequency $^{85}$Rb alkali-vapor cell magnetometer based on a paraffin-coated cell with long spin-coherence time and a small, low-inductance driving coil to create highly resolved conductivity maps of different objects. We resolve sub-mm features in conductive objects, we characterize the frequency response of our technique, and by operating at frequencies up to 250 kHz we are able to discriminate between differently conductive materials based on the induced response. The method is suited to cover a wide range of driving frequencies and can potentially be used for detecting non-metallic objects with low DC conductivity.

physics.ins-det↗

Measurement of Untruncated Nuclear Spin Interactions via Zero- to Ultra-Low-Field Nuclear Magnetic Resonance

Zero- to ultra-low-field nuclear magnetic resonance (ZULF NMR) provides a new regime for the measurement of nuclear spin-spin interactions free from effects of large magnetic fields, such as truncation of terms that do not commute with the Zeeman Hamiltonian. One such interaction, the magnetic dipole-dipole coupling, is a valuable source of spatial information in NMR, though many terms are unobservable in high-field NMR, and the coupling averages to zero under isotropic molecular tumbling. Under partial alignment, this information is retained in the form of so-called residual dipolar couplings. We report zero- to ultra-low-field NMR measurements of residual dipolar couplings in acetonitrile-2-$^{13}$C aligned in stretched polyvinyl acetate gels. This represents the first investigation of dipolar couplings as a perturbation on the indirect spin-spin $J$-coupling in the absence of an applied magnetic field. As a consequence of working at zero magnetic field, we observe terms of the dipole-dipole coupling Hamiltonian that are invisible in conventional high-field NMR. This technique expands the capabilities of zero- to ultra-low-field NMR and has potential applications in precision measurement of subtle physical interactions, chemical analysis, and characterization of local mesoscale structure in materials.

physics.chem-ph↗

Long-lived heteronuclear spin-singlet states

We report observation of long-lived spin-singlet states in a 13C-1H spin pair at zero magnetic field. In 13C-labeled formic acid, we observe spin-singlet lifetimes as long as 37 seconds, about a factor of three longer than the T1 lifetime of dipole polarization in the triplet state. We also observe that the lifetime of the singlet-triplet coherence, T2, is longer than T1. Moreover, we demonstrate that this singlet states formed by spins of a heteronucleus and a 1H nucleus, can exhibit longer lifetimes than the respective triplet states in systems consisting of more than two nuclear spins. Although long-lived homonuclear spin-singlet states have been extensively studied, this is the first experimental observation of analogous spin-singlets consisting of a heteronucleus and a proton.

physics.chem-ph↗