Richard W. Quine

Pulsed EPR spectrometer

A pulsed EPR spectrometer is described. This spectrometer is designed for the study of relaxation times of dilute solutions of samples in common solvents as a function of temperature both above and below room temperature. Resolution of pulse widths and spacings is 1 ns. Both continuous wave (cw) and pulsed electron spin‐echo studies can be done on the same sample on the same spectrometer. Details of component choices and timing synchronization are provided. Phase alternation sequences for eliminating unwanted echoes are described. Examples of performance of the spectrometer are presented.

Saturation recovery electron paramagnetic resonance spectrometer

A versatile saturation recovery accessory based on a small, special‐purpose timing controller and an efficient mix of coaxial and waveguide microwave components has been added to a commercial electron paramagnetic resonance (EPR) spectrometer. The spectrometer was designed for study of the spin lattice relaxation time of transition metals and free radicals over a wide temperature range, such as are of interest in materials science and metallobiochemistry. A microprocessor‐based timing system was designed to provide a wide dynamic range with a simple user interface. Waveguide phase shifters and rotary vane attenuators were used for their precision and resetability, while coaxial components were used where their superior performance could be exploited. Sensitivity is provided by a low‐noise GaAs field‐effect transistor (FET) microwave preamplifier and a double‐balanced mixer (DBM) detector. A biphase modulator (±180° phase shifter) on the lo side of the DBM provided efficient addition/subtraction of success...

Deconvolution of sinusoidal rapid EPR scans

In rapid scan EPR the magnetic field is scanned through the signal in a time that is short relative to electron spin relaxation times. Previously it was shown that the slow-scan lineshape could be recovered from triangular rapid scans by Fourier deconvolution. In this paper a general Fourier deconvolution method is described and demonstrated to recover the slow-scan lineshape from sinusoidal rapid scans. Since an analytical expression for the Fourier transform of the driving function for a sinusoidal scan was not readily apparent, a numerical method was developed to do the deconvolution. The slow scan EPR lineshapes recovered from rapid triangular and sinusoidal scans are in excellent agreement for lithium phthalocyanine, a trityl radical, and the nitroxyl radical, tempone. The availability of a method to deconvolute sinusoidal rapid scans makes it possible to scan faster than is feasible for triangular scans because of hardware limitations on triangular scans.

A 1–2 GHz pulsed and continuous wave electron paramagnetic resonance spectrometer

A microwave bridge has been constructed that performs three types of electron paramagnetic resonance experiments: continuous wave, pulsed saturation recovery, and pulsed electron spin echo. Switching between experiment types can be accomplished via front‐panel switches without moving the sample. Design features and performance of the bridge and of a resonator used in testing the bridge are described. The bridge is constructed of coaxial components connected with semirigid cable. Particular attention has been paid to low‐noise design of the preamplifier and stability of automatic frequency control circuits. The bridge incorporates a Smith chart display and phase adjustment meter for ease of tuning.

X-band rapid-scan EPR of nitroxyl radicals

X-band rapid-scan EPR spectra were obtained for dilute aqueous solutions of nitroxyl radicals (15)N-mHCTPO (4-hydro-3-carbamoyl-2,2,5,5-tetra-perdeuteromethyl-pyrrolin-1-(15)N-oxyl-d(12)) and (15)N-PDT (4-oxo-2,2,6,6-tetra-perdeuteromethyl-piperidinyl-(15)N-oxyl-d(16)). Simulations of spectra for (15)N-mHCTPO and (15)N-PDT agreed well with the experimental spectra. As the scan rate is increased in the rapid scan regime, the region in which signal amplitude increases linearly with B(1) extends to higher power and the maximum signal amplitude increases. In the rapid scan regime, the signal-to-noise for rapid-scan spectra was about a factor of 2 higher than for unbroadened CW EPR, even when the rapid scan spectra were obtained in a mode that had only 4% duty cycle for data acquisition. Further improvement in signal-to-noise per unit time is expected for higher duty cycles. Rapid scan spectra have higher bandwidth than CW spectra and therefore require higher detection bandwidths at faster scan rates. However, when the scan rate is increased by increasing the scan frequency, the increase in noise from the detection bandwidth is compensated by the decrease in noise due to increased number of averages per unit time. Because of the higher signal bandwidth, lower resonator Q is needed for rapid scan than for CW, so the rapid scan method is advantageous for lossy samples that inherently lower resonator Q.

A hydrocarbon detector for the remote sensing of vehicle exhaust emissions

A new remote sensor for measuring on‐road carbon monoxide, carbon dioxide, and hydrocarbon exhaust emissions in under 1 s from vehicles passing the sensor is described. The new design adds the capability for measuring exhaust hydrocarbons and eliminates the need for liquid–nitrogen‐cooled detectors while improving upon the overall signal to noise. Under typical field operating conditions, sensitivity to 0.05% propane with a precision of 0.014% propane is observed. Two types of water interferences important to the measurement of exhaust hydrocarbons are reported. The water vapor present in all auto exhaust causes a small positive bias dependent on the analytical wavelength chosen. A much larger interference is caused by liquid water (often called ‘‘steam’’) plumes seen behind cold vehicles at low temperatures.

Frequency Dependence of EPR Sensitivity

Contrary to some prior derivations, it is shown that the sensitivity of EPR measurements is, as expected, the same as for NMR, and that in general comparisons of EPR sensitivity as a function of frequency have been pessimistic by one factor of ω. The sensitivity of EPR can increase at lower frequency if the sample size is scaled inversely with frequency.

X-band rapid-scan EPR of samples with long electron spin relaxation times: a comparison of continuous wave, pulse and rapid-scan EPR

X-band room temperature spectra obtained by rapid-scan, continuous wave, field-swept echo-detected and Fourier transform electron paramagnetic resonance (FTEPR) were compared for three samples with long electron spin relaxation times: amorphous hydrogenated silicon (T1 = 11 μs, T2 = 3.3 μs), 0.2% N@C60 solid (T1 = 120–160 μs, T2 = 2.8 μs) and neutral single substitutional nitrogen centres (NS0) in diamonds (T1 = 2300 μs, T2 = 230 μs). For each technique, experimental parameters were selected to give less than 2% broadening of the lineshape. For the same data acquisition times, the signal-to-noise for the rapid-scan spectra was one-to-two orders of magnitude better than for continuous wave or field-swept echo-detected spectra. For amorphous hydrogenated silicon, T2* (∼ 10 ns) is too short to perform FTEPR. For 0.2% N@C60, the signal-to-noise ratio for rapid scan is about five times better than for FTEPR. For NS0 the signal-to-noise ratio is similar for rapid scan and FTEPR.

Background removal procedure for rapid scan EPR

In rapid scan EPR the changing magnetic field creates a background signal with components at the scan frequency and its harmonics. The amplitude of the background signal increases with scan width and is more significant for weak EPR signals such as are obtained in the presence of magnetic field gradients. A procedure for distinguishing this background from the EPR signal is proposed, mathematically described, and tested for various experimental conditions.

Imaging of nitroxides at 250 MHz using rapid-scan electron paramagnetic resonance

Projections for 2D spectral-spatial images were obtained by continuous wave and rapid-scan electron paramagnetic resonance using a bimodal cross-loop resonator at 251MHz. The phantom consisted of three 4mm tubes containing different (15)N,(2)H-substituted nitroxides. Rapid-scan and continuous wave images were obtained with 5min total acquisition times. For comparison, images also were obtained with 29s acquisition time for rapid scan and 15min for continuous wave. Relative to continuous wave projections obtained for the same data acquisition time, rapid-scan projections had significantly less low-frequency noise and substantially higher signal-to-noise at higher gradients. Because of the improved image quality for the same data acquisition time, linewidths could be determined more accurately from the rapid-scan images than from the continuous wave images.