Influence of the movement of cylindrical samples with variable internal diameter and variable length along the x-axis of a double TE104 and a single TE102 rectangular cavity on the EPR signal intensity: A sample shape study
M. Mazur et al., Influence of the movement of cylindrical samples with variable internal diameter and variable length along the x-axis of a double TE104 and a single TE102 rectangular cavity on the EPR signal intensity: A sample shape study, APPL MAGN R, 20(3), 2001, pp. 317-344
The response of the cavity to the movement of cylindrical samples with inte
rnal diameters from 0.7 to 4 mm and lengths from 5 to 50 mm along the x-axi
s of the Bruker double TE104 and single TE102 rectangular cavity has been a
nalyzed. Independently of sample internal diameter, the experimentally obse
rved dependences of the electron paramagnetic resonance (EPR) signal intens
ity versus sample position in the cavity showed the following: (i) a sharp
maximum for sample lengths from 5 to 20 mm; (ii) a "plateau", over which th
e signal intensity remained constant within experimental errors of 0.47-1.1
6%, for lengths from 30 to 40 mm; and (iii) a "sloping plateau" region, whi
ch could be approximated by the linear function (correlation r = 0.96-0.98)
for the 50 mm sample. Theoretical predictions of the experimental dependen
ces of the signal intensity versus sample position in the cavity were calcu
lated with the "modified" and "'revised" sine-squared function, and the cor
relation between observed and theoretically computed dependences is very go
od. Additionally, the experimental dependence of the signal intensity versu
s the sample internal diameter and length for cylindrical samples situated
at the position in the cavity at which the signal intensity was a maximum w
as likewise numerically approximated by the surface fitting with the Lorent
zian cumulative additive function (correlation r = 0.999). The experimental
dependence of the signal intensity versus the sample internal diameter for
the given sample length is nonlinear. The samples with internal diameters
of 0.7 and 1 mm gave the total maximum of signal intensity for the 40 mm sa
mple, however, the samples with internal diameters of 2, 3 and 4 mm gave th
e total maximal value of signal intensity, which was identical for both the
30 and 40 mm samples. The experimental dependence of the EPR signal intens
ity versus the sample volume clearly showed that the samples with identical
volumes, however, with different shapes, can give significantly different
signal intensities (with differences ca. 200-400%). Then, the comparison of
cylindrical samples with identical volumes but different shapes may be a s
erious source of significant errors in quantitative EPR spectroscopy Cylind
rical samples to be compared should he of identical shape. Accurate and pre
cise positioning of each sample in the microwave cavity is essential.