Experiment 15.

Electron Spin Resonance

Updated RWH 15 March 2008

Objectives

The aim of this experiment is to measure the properties of Electron Spin Resonance (ESR) in two organic compounds, and to devise a method using ESR to determine the magnitude and direction of the Earths magnetic eld at Sydney.

Introduction

The idea of electron spin and its associated magnetic moment was rst introduced by George Uhlenbeck and Samuel Goudsmit1 to explain ne structure in optical spectra. These new properties which the electron seemed to possess were put on a sound theoretical basis a few years later in a landmark paper by Paul Dirac in 1928. 2 A proper relativistic quantum mechanical treatment of the hydrogen atom leads naturally to the electron possessing, in addition to its mass m and charge e, an intrinsic or spin angular momentum with quantum number s = 1/2. The spin vector S has magnitude 3 s(s + 1) = h h. 2

S=
1 2

(1)

G.E. Uhlenbeck & S. Goudsmit, Naturwissenschaften, 47, 954 (1925) P.A.M. Dirac, The quantum theory of the electron, Proc. Roy. Soc. London A, 117, 610 (1928)

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In the presence of a magnetic eld, the component of spin parallel to the eld (z direction) is quantised. It has two possible values, 1 Sz = m s h = h . 2 The possible orientations of S relative to the z direction are shown in Fig. 15-1. (2)

Fig. 15-1 : Vector model for electron spin

Since an electron has both charge and angular momentum, it also has a magnetic moment, s , proportional to the angular momentum, where s = g e S. 2m (3)

According to Diracs theory, g is precisely 2. The measured value, g = 2.00232, arises in quantum electrodynamics (QED) from the electrons anomalous magnetic dipole moment. Quantisation of spin leads to quantisation of the corresponding magnetic moment. The component values for magnetic moment are e Sz = gms B = gB /2, (4) 2m where B is the Bohr magneton, e /2m. In the presence of a magnetic eld B, there is potential h energy U associated with the orientation of the magnetic moment relative to the magnetic eld, given by sz = g U = s B = sz B = gB B/2. (5)

The energy difference between the two electron states is given by U = gB B. (6)

E LECTRON S PIN R ESONANCE Transitions between these states can be produced by photons of frequency r , given by

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hr = gB B.

(7)

Free radicals

In principle, we could take a group of electrons in a magnetic eld B and induce them to make transitions from one ms state to the other using a radio frequency eld of frequency r . This would be difcult as electrons repel each other and, in any case, they would describe circular orbits at the cyclotron resonance frequency eB/(2m). However, a solid source of electrons is obtained from an organic chemical called a free radical: the two which will be examined in this experiment are diphenyl picryl hydrazyl (DPPH) and tetracyanoquinodimethane (TCNQ). Their chemical makeup is shown in Fig. 15-2. These substances contain electrons which act as though they were free. Free radicals thus exhibit g-factors very close to the value for a free electron, 2.0023. In fact, the fractional difference is less than one part in a thousand. Any shift in g would arise from an interaction between the electron magnetic moment and the overall magnetic moment of the molecule. We would expect a shift equal to or less than the ne structure shift in the H atom, and this quantity is of the order of one part in a thousand.

Fig. 15-2 : Chemical structure of the free radicals TCNQ (left) and DPPH (right)

Electron spin resonance in TCNQ and DPPH can be shown with the sample held in a small coil and placed in a uniform magnetic eld. The coil (inductance L) is connected in parallel with a capacitor C to make an LC resonant circuit. At the resonant frequency, r = geB/(4m), energy must be supplied by the circuit in order to change the spin state of the electrons from one value of m s to the other. As a result there will be a minute decrease in the Q or quality factor of the resonant circuit. 1 When the circuit is set up to oscillate weakly at a frequency (= 2 LC) the electron spin resonance is readily seen because the tiny decrease in the Q of the resonant circuit can be easily detected by the amplifying electronics. 3 Sweeping through the resonance is best done by varying B, since it is electronically more difcult to sweep through in frequency and maintain a constant amplitude. In our case, the eld is produced by a Helmholtz coil (see Section 4.3 and page 79 of the bench manual for further explanation of the Helmholtz coil).
1 L Note: the Q of a parallel-tuned LC circuit is given by Q = R C . The excitation of ESR causes a slight increase in loading of the tuned circuit and a corresponding increase in the effective value of R. 3

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The apparatus

The manual for the spectrometer you will be using is on the bench and has also been placed as a PDF le (named CWS 12 50 manual) on the computer. The pages relevant to the ESR experiment are 19, 2541, 55, 7172, 79, and 82. Figure 15-3 shows a schematic diagram of the ESR spectrometer.

Fig. 15-3 : Schematic diagram of the electron spin resonance experiment. The reference to NMR (nuclear magnetic resonance) is not relevant for this experiment.

The sample is placed in a coil, inductance L, in parallel with a capacitor C. This is the resonant circuit (also called a tank circuit), which oscillates at 50 MHz. The phase-locked loop (PLL) is a feedback circuit that adjusts the value of the capacitance until the circuit is locked onto the preset frequency. The variable capacitor is a reverse-biased diode, known as a varactor diode, in which C depends on the thickness of the charge depletion layer; this is controlled by adjusting the applied voltage.

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4.1

Differential detection

The principle of resonance detection is simply to detect a change in the amplitude of oscillations in this coil. This is achieved by varying the applied magnetic eld in a sinusoidal manner at 38 Hz. The 50 MHz frequency is ltered on the detection side of the electronics and only the signal amplitude difference (due to the 38 Hz modulation of B) is passed on to the detection amplier. A consequence of this sensitive detection method is that a differentiation of the resonance (or absorption) signal is obtained. The characteristic prole of a forced resonance, either that of a damped LC circuit or a natural transition in an atom or electron, is known as a Lorentzian. The Lorentzian function is given by

L() =

1 1 2 , 1 ( 0 )2 + ( 2 )2

(8)

with full width at half maximum (FWHM) equal to . In this experiment we keep the frequency xed and vary B, but the form of the equation is the same, with replaced by B, as shown in Fig. 15-4. By convention, Fig. 15-4 is shown in emission rather than absorption.

Fig. 15-4 : The Lorentzian line shape of an absorption (resonance) line.

The detected signal is the derivative of the Lorentzian line prole, as shown in Fig. 15-5. Differential detection enables the precise position of the absorption peak to be determined, since it corresponds to the point where the differential signal equals zero (i.e., the zero-crossing). Moreover, one commonly-used measure of the line width of the Lorentzian can easily be obtained from the separation between the positive and negative going peaks in the differentiated signal. Although the software that operates the spectrometer can do the analysis for obtaining the zero crossing, line width, and integrating to obtain the absorption signal, you are required to carry this out for yourself and present the graphs and analysis in your logbook. You can do this easily with the ORIGIN software package.

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Fig. 15-5 : The derivative of the absorption signal shown in Fig. 15-4. This is the form of the signal received from the spectrometer.

4.2 Signicance of line-width

The natural width of an ESR spectral line is a measure of its interaction with its environment. That is, the electrons not only interact with the applied magnetic eld but any other magnetic eld arising from their environment such as those from other electron or nuclear spins. So ESR can be an excellent probe of the electronic or nuclear magnetic environment. The line becomes broader with increasing coupling of the electrons to their environment.

4.3 Helmholtz coil

Helmholtz coils consist of two coaxial coils of the same radius, in series and spaced a distance apart equal to their radius. For this conguration the eld is particularly uniform over a small region at the centre of the conguration. The magnetic eld supplied by the Helmholtz coils is shown schematically in Fig. 15-6. A uniform magnetic eld of variable strength is often needed in physics. For a large eld this is best done with an electromagnet whose core is composed of a magnetic material of high relative permeability and with at parallel pole pieces. If this technique is used for small elds (as required in this experiment) a difculty arises because all magnetic materials have a remanent eld: a nite eld is present even when the magnetising current is zero, making the setting of reproducible elds difcult.

4.4 Dip circle

The dip circle, shown in Fig. 15-7, is a compass that enables the Earths magnetic eld direction to be determined. Ordinary compasses allow you to determine the direction of the Earths eld in the horizontal plane. In reality, the Earths eld makes an angle in the vertical plane. The dip circle allows you to determine this angle since it can swivel in both the horizontal and vertical planes.

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Fig. 15-6 : Helmholtz coils, showing the uniformity of the magnetic eld in the central region. [from The Physics of Electricity and Magnetism, W.T. Scott (Wiley, 1962)]

Fig. 15-7 : The dip circle gives the angle of the Earths magnetic eld.

Experimental Procedure
1. Make sure that the spectrometer is connected as shown on page 19 of the bench manual, and that the TCNQ sample is fully inserted in the Probehead. The Helmholtz coil and Probehead combination are xed to a Perspex sheet making it easier to rotate the assembly later in the experiment. For this rst part of the experiment the orientation is not important. 2. Start the CWNE software. This brings up the Startup and Acquisition page with a comprehensive menu for data acquisition. Click on Spectrometer then on Connect in the top menu. This establishes a connection between the computer and the spectrometer. It will also automatically switch to the ESR mode and will indicate this by a red light next to ESR on the probehead. Select Single (for a single scan) and let Acc be initially 1 (for one scan) in the bottom right hand corner of the screen. Set the Field Sweep to 5 gauss (Gs)4 and leave the 2nd Mod Amplit and Sweep Time at their default values of 0.05 Gs and 0.5 min respectively. 3. Clicking on the Start button in the Acquisition section will start the 30-second scan. You should obtain a differential plot as described in section 4.1. This will probably be a bit noisy. Vertical scaling can be adjusted with the Gain control and the DC offset with the slider control on the left of the screen. Experiment with both controls until you are satised with the result. 4. You are now ready to collect data. First you need to create your own subdirectory in the Student les directory. Then switch back to the Acquisition screen and, under Tools File location, tell the software where to put your data by typing the directory path for both acquisition and data output.
4

The gauss is the unit of magnetic eld in the old cgs system: 1 Gs = 104 T.

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5. To reduce the noise in the signal it is simplest to average several scans. To do this, increase the number next to Acc to around 5 or more and depress the Acc button in the upper left hand part of the screen. Pressing Start will then do the averaging. 6. When you have obtained a spectrum you are happy with, you can save it from the File menu on the top left hand corner of the screen. The le will be saved in your subdirectory with a .dcw extension. 7. This saved spectrum can now be processed by clicking on the Proc button at the top of the screen. This will take you to another screen with upper and lower graph panels. Click on the Open File button and load your saved le into the top panel. Now click on the 1st Derivative button on the top left hand side of the screen to load this into the bottom panel. You are now ready to make some basic measurements on this spectrum using the inbuilt software. 8. The VE button above the bottom graph panel autoscales the spectrum in the vertical direction, and the G button alongside calculates the g-value, which is displayed on the bottom right hand side of the screen. 9. There are two ways of measuring the linewidth: (i) the separation between the points of inection, which is given by the SDB button, and (ii) the full width at half maximum (FWHM) of the absorption prole. The latter measurement is obtained by clicking the Absorption button at the top of the screen this integrates the 1st derivative spectrum and then the HDB button above the lower panel. Record the values of g, SDB, HDB and position of the absorption peak (or zero-crossing in the differential plot) in your logbook, along with any other relevant information about the dataset. 10. You now need to save the 1st derivative data for later input to ORIGIN by clicking on the Export ASCII button at the top of the screen; the le name is the same as before, but with a .txt extension. The le will be located in the directory you specied earlier. 11. Finally, go through the procedure above for the DPPH sample with the Field Sweep set to 15 Gs.

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5.1

Lorentzian prole

In this section we will analyse the 1st derivative data using ORIGIN and test whether the absorption prole is indeed Lorentzian, as we have assumed. 1. Import the TCNQ .txt le into ORIGIN with the File Import Single ASCII menu and plot the le. 2. Use the Integrate function in ORIGIN to obtain the absorption prole. Then use the Baseline function to t to any sloping baseline using the end-weighting option. Subtract the tted baseline to give a clean prole with a nominal baseline of zero. 3. Fit a Lorentzian to the absorption prole and save a properly labelled hardcopy. Compare the parameters of the t, notably the peak position and FWHM, with those obtained earlier. Comment on the goodness of t, as measured by the reduced 2 . Experience suggests that the formal t errors may be underestimated. 4. Repeat the above treatment for the DPPH data. Which of the two samples has electrons more strongly coupled to the environment? Question: Using Eqn. 8 show that the relationship between the separation of the points of inection (SDB) and the FWHM (HDB) is given by SDB = HDB/ 3.

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5.2 Measurement of the Earths Magnetic Field

The Geographic North Pole is actually a magnetic South Pole as shown in Fig. 15-8

Fig. 15-8 : Geographic north and south poles are actually magnetic south and north poles, respectively. Note that the magnetic eld lines at Sydney emerge at an angle to the Earths surface.

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Use the dip circle to determine the direction of the horizontal component of the the Earths magnetic eld and the angle of dip in this plane. You will need this later when determining the magnitude of this eld. Turn off the Helmholtz coils and keep the compass away any iron objects so as not to distort the direction of the eld.

5.3 Determination of the Earths magnetic eld and the electron g-value
If it wasnt for the Earths magnetic eld, it would be a simple matter to nd the g-value by obtaining the resonant frequency and using Eqn. 7. However, the Earths eld will add to or subtract from the applied eld from the Helmholtz coil, depending on the orientation of the axis of symmetry of the coil with respect to the horizontal component of the Earths eld. Note that the axis of symmetry of the Helmholtz coil is in the horizontal plane. If the horizontal component of the Earths eld is parallel to the axis of the Helmoltz coil, then the two elds will add and this combined eld will be applied to the electrons. However, if these two elds are antiparallel the horizontal component of the Earths eld will subtract from the applied eld. Ideally, these two congurations will produce resonant peaks symmetric about an applied eld of zero; if they dont there may be a small systematic error in the assumed B eld from the Helmholtz coils. Now devise a method that will accurately determine the g-value of the electron as well as the horizontal component of the Earths magnetic eld. Explain how you will use the angle of dip measured with the dip circle to determine the magnitude of the Earths magnetic eld. Outline your method in your logbook and get a demonstrator to check before proceeding.

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5.3.1 Results and Analysis

Carry out your experiment using the TCNQ sample, save your results and analyse using ORIGIN, including errors in your analysis. Remember to use the accumulate feature in the acquisition program if you need to reduce any noise. Use your results to determine values for g and the total magnetic eld of the Earth. Compare your results for the Earths magnetic eld with the accurate values from the online calculator at the National Geophysical Data Center (www.ngdc.noaa.gov/seg/geomag/jsp/IGRFWMM.jsp; select country and city) and comment. Write a conclusion.

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