Search

In this work, we demonstrate the first pulsed electron paramagnetic resonance (EPR) experiments performed under magic angle spinning (MAS) at high magnetic field. Unlike nuclear magnetic resonance (NMR) and dynamic nuclear polarization (DNP), commonly performed at high magnetic fields and under MAS to maximize sensitivity and resolution, EPR is usually measured at low magnetic fields and, with the exception of the Spiess group work in the late 1990s, never under MAS, due to great instrumentational challenges. This hampers the investigation of DNP mechanisms, in which electron spin dynamics play a central role, because no experimental data about the latter under DNP-characteristic conditions are available. We hereby present our dedicated, homebuilt MAS-EPR probehead and show the pulsed MAS-EPR spectra of P1 center diamond defect recorded at 7 tesla. Our results reveal unique effects of MAS on EPR line shape, intensity, and signal dephasing. Time-domain simulations reproduce the observed changes in the line shapes and the trends in the signal intensity.

We report the finding of doubly charged molecular ions in a range of relatively large molecules including hydrocarbons upon their electron ionization as vibrationally cold molecules in supersonic molecular beams (SMB) (also named as Cold EI). Furthermore, we also report the detection by mass spectrometry of triply charged molecular ions in large PAHs such as decacyclene and ovalene upon their cooling in SMB. We found that the relative abundance of doubly charged molecular ions strongly depends on the internal vibrational cooling. While after some vibrational cooling the fragmentation pattern became cooling independent, the relative abundance of the doubly charged molecular ions was noticeably increased upon further cooling via increasing of the cooling make-up gas flow rate. In addition, the relative abundance of the doubly charged molecular ions was strongly increased with the compounds' size, and its electron energy threshold was lower than expected. These observations indicate a new mechanism that involves two separate electron ionization processes in the same compound, most likely with the same electron but at two separate atoms (places) in large molecules, to reduce Coulombic repulsion energy that can lead to fragmentation into two singly charged ions. These findings are shedding new light on electron ionization mass spectra. Accordingly, electron ionization mass spectra are the result of three separate mechanisms with relative magnitudes that depend on the compound size: (a) single electron ionization; (b) double electron ionization; and (c) single electron ionization with subsequent internal excitation by the same ionizing electron in another place.