Tobias F. Sjolander

Spectroscopic observation of resonances in the F + H2 reaction

Glimpsing resonances as F and H2 react The reaction of fluorine atoms with hydrogen molecules has long provided a window into the subtle effects of quantum mechanics on chemical dynamics. Kim et al. now show that the system still has some secrets left to reveal. The authors applied photodetachment to FH2− anions and their deuterated analogs. This allowed them to intercept the reaction trajectory in the middle and thereby uncover unanticipated weakly bound resonances. Theoretical calculations explain these observations and predict additional similar features that have yet to be seen. Science, this issue p. 510 Combined theory and experiment uncover subtle weakly bound states along the pathway of a widely studied chemical reaction. Photodetachment spectroscopy of the FH2− and FD2− anions allows for the direct observation of reactive resonances in the benchmark reaction F + H2 → HF + H. Using cooled anion precursors and a high-resolution electron spectrometer, we observe several narrow peaks not seen in previous experiments. Theoretical calculations, based on a highly accurate F + H2 potential energy surface, convincingly assign these peaks to resonances associated with quasibound states in the HF + H and DF + D product arrangements and with a quasibound state in the transition state region of the F + H2 reaction. The calculations also reveal quasibound states in the reactant arrangement, which have yet to be resolved experimentally.

Measurement of untruncated nuclear spin interactions via zero- to ultralow-field nuclear magnetic resonance

Author(s): Blanchard, JW; Sjolander, TF; King, JP; Ledbetter, MP; Levine, EH; Bajaj, VS; Budker, D; Pines, A | Abstract:

Nuclear magnetic resonance at millitesla fields using a zero-field spectrometer.

We describe new analytical capabilities for nuclear magnetic resonance (NMR) experiments in which signal detection is performed with chemical resolution (via spin-spin J couplings) in the zero to ultra-low magnetic field region, below 1μT. Using magnetic fields in the 100μT to 1mT range, we demonstrate the implementation of conventional NMR pulse sequences with spin-species selectivity.

Transition-Selective Pulses in Zero-Field Nuclear Magnetic Resonance

We use low-amplitude, ultralow frequency pulses to drive nuclear spin transitions in zero and ultralow magnetic fields. In analogy to high-field NMR, a range of sophisticated experiments becomes available as these allow narrow-band excitation. As a first demonstration, pulses with excitation bandwidths 0.5-5 Hz are used for population redistribution, selective excitation, and coherence filtration. These methods are helpful when interpreting zero- and ultralow-field NMR spectra that contain a large number of transitions.

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 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 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.

Invited Review Article: Instrumentation for nuclear magnetic resonance in zero and ultralow magnetic field

We review experimental techniques in our laboratory for nuclear magnetic resonance (NMR) in zero and ultralow magnetic field (below 0.1 μT) where detection is based on a low-cost, non-cryogenic, spin-exchange relaxation free 87Rb atomic magnetometer. The typical sensitivity is 20-30 fT/Hz1/2 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 ultralow magnetic fields.

13C-Decoupled J-Coupling Spectroscopy Using Two-Dimensional Nuclear Magnetic Resonance at Zero-Field

We present a two-dimensional method for obtaining 13C-decoupled, 1H-coupled nuclear magnetic resonance (NMR) spectra in zero magnetic field using coherent spin-decoupling. The result is a spectrum determined only by the proton-proton J-coupling network. Detection of NMR signals in zero magnetic field requires at least two different nuclear spin species, but the proton J-spectrum is independent of isotopomer, thus potentially simplifying spectra and thereby improving the analytical capabilities of zero-field NMR. The protocol does not rely on a difference in Larmor frequency between the coupled nuclei, allowing for the direct determination of J-coupling constants between chemically equivalent spins. We obtain the 13C-decoupled zero-field spectrum of [1-13C]-propionic acid and identify conserved quantum numbers governing the appearance of cross peaks in the two-dimensional spectrum.