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On Electron Paramagnetic Resonance in DPPH

Shane Duane ID: 08764522 JS Theoretical Physics 5th Dec 2010

Abstract Electron Paramagnetic Resonance (EPR) was investigated in diphenyl pecryl hydrazyl (DPPH). The Helmholtz EM coil arrangement was shown to have a linear relationship between eld strength and current. A value of g = 1.85 was found for the electron g-factor, in reasonble agreement with [2]. This also validated the theory of EPR as in Weil [1].

Introduction & Theory

For a more detailed discussion of the theory behind this experiment see chapter 1 of [1]. The spin of the electron is one of its intrinsic properties. It has an associated spin angular momentum which can only take values MS h, where MS = 1/2. Since the electron is charged the spin angular momentum has an associated magnetic moment and its component z along the direction z of a magnetic eld B is z = e hMS = gB MS (1) where e is the gyromagnetic ratio, B = 9.2740 1024 J T1 [1] is the Bohr magneton and g = 2.002319 [2] is the free electron g -factor, a dimensionless quantity. The energy U of a magnetic dipole of moment in a magnetic eld B is U = .B. For the electron, (2) becomes U = gB BMS , (3) (2)

hence with the eld being static there are two energy levels diering in energy by U = gB B. (4) The splitting of the energy levels is known as Zeeman splitting. If an electromagnetic eld B1 supplies photons of frequency such that U = h , then the photons can induce a transition between the spin states of the electron where the resonance condition is h = gB B. (5)

This ipping over of electron spin magnetic moments is known as electron spin resonance (ESR). More generally, there may be an orbital contribution to so that the term electron paramagnetic resonance (EPR) is also used. In this experiment the sample used was diphenyl pecryl hydrazyl (DPPH), an organic radical which gives a single line EPR spectrum. For EPR a very stable uniform static eld B must be used, as variations in B will lead to variations in energy separations U . If B is not uniform over the sample, then the spectral lines will be broadened. Hence a Helmholtz coil arrangement was used as it provides the most uniform eld achievable with two electromagnetic (EM) coils. The eld B at distance x from the centre on the axis of a single coil of radius r with N turns is B= 0 N Ir2 . 2(x2 + r2 )3/2 (6)

The eld on the axis between a pair of coils at a distance x from one of them is B= 1 1 1 0 r2 I + , 2 2 3 / 2 2 2 (x + r ) (( x) + r2 )3/2 (7)

where is the separation between the coils. An attempt to prove that the most uniform eld occurs for = r was made, but was unsuccessful.

Experimental Method

Section I Field Prole on Axis of EM Coils & B (I ) Calibration A Hall probe was used to measure the steady eld B between the coils. The coils used had an adjustable spacing so B was measured for three values of . The current was kept steady at 0.5 A. The eld was found to be most uniform for a coil spacing of = r. Hence the dependence of B on I was measured in the range 0.1 0.7 A for 69mm. Section II Resistance & Impedance of EM Coils The total resistance R and impedance Z of the two coils was determined using a multimeter. To nd Z we measured Vcac , the AC potential dierence across the coils, and Icac , the AC current running through the coils. Section III To measure B ( ) and nd g for DPPH The circuit was set up as in Fig. 1 where the EPR module generated the oscillating eld B1 from its RF coil of inductance L. In the module was a variable capacitance C connected in parallel with the coil. The frequency 0 = 1/(LC )1/2 of the circuit could be changed by adjusting C . When 0 = we had resonance. The current was measured for 10 values of and used to plot B vs in Graph 5. Section IV This section was not attempted since time did not allow. Section V This section was not attempted since time did not allow. 2


Errors e in the nal signicant gures of results are denoted by the error magnitude in brackets: (e). Section I Field Prole on Axis of EM Coils & B (I ) Calibration The results for B vs are plotted in Graphs 1 to 3. In Graph 4 we see a plot of B vs I for = 69 mm. The slope here is B/I = 0.00352(1) T/A. The calculated value for B/I using (7) was of the order 105 , which is not in agreement. However, if the formula (6) for a single coil is used and doubled to account for the two coils we nd B/I = 0.00291 which is much closer to the experimental value. Section II Resistance & Impedance of EM Coils The resistance R of the two coils in series was found to be 13.8(1) . The coil AC current and voltage were found to be Icac = 0.124(1) A and Vcac = 2.53(1) V, respectively. These gave an impedance Z = Vcac /Icac = 20.4(1). Section III To measure B ( ) and nd g for DPPH The data for B vs is plotted in Graph 5. The ratio B/ = 3.86(5) 1011 T/Hz gives a value g = 1.85 from (5).


An error must have been made in the theoretical understanding of the Helmholtz arrangement due to the inability of (7) to predict the B/I ratio. the relationship between B and I was shown to be linear in Graph 4, agreeing both with (6) & (7). The value of g = 1.85 found agrees to within 7% of the accepted value from [2], which veries the theory of spin transitions and (5).

1. Electron Paramagnetic Resonance, J.A. Weil et al. 2. NIST Reference on Constants, Units & Uncertainty,

Appendix: Figures & Graphs

Figure 1: Circuit Diagram for Section III

Figure 2: Field versus position for 40mm spacing

Figure 3: Field versus position for 69mm spacing

Figure 4: Field versus position for 100mm spacing

Figure 5: Field versus current for 69mm spacing

Figure 6: Field versus frequency at resonance