Experiment 15.

Electron Spin Resonance

Equipment list:1. 2. 3. 4. 5. 6. 7. 8. CWS 12-50 Manual (see pages 19 and 21 for equipment picture) NMR/ESR spectrometer console (the box) Probehead (this is where the sample is placed) Helmholtz coils Sample of DPPH (2,2-Diphenyl-1-Picrylhydrazyl) Sample of TCNQ (7,7,8,8-tetracyanoquinodimethane) Dip circle (to nd direction of earths magnetic eld) Computer and CWNE software.

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1 Objectives
The aim of this experiment is to use Electron Spin Resonance (ESR) to measure the g value of free electrons and to use this to determine the magnitude of the Earths magnetic eld.

2 Introduction
The idea of electron spin and its associated magnetic moment was introduced by Uhlenbeck and Goudsmit 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 by Dirac in 1928. 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)

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 = ms 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 , is proportional to the angular momentum.

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s = g

e S 2m

(3)

According to Diracs theory g = 2. The measured value, g = 2.00232, is explained by quantum electrodynamics (QED). Quantisation of spin leads to quantisation of magnetic moment. The component values for magnetic moment are sz = g e Sz = gms B = gB /2 2m (4)

In the presence of a magnetic eld there is potential energy associated with the orientation of the magnetic moment relative to the magnetic eld given by E = s B = sz B = gB B/2 The energy difference between the two electron states is given by E = gB B Transitions between these states can be produced by photons of frequency r given by hr = gB B (7) (6) (5)

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: diphenyl picryl hydrazyl (dpph). This substance contains electrons which act as though they were free. Free radicals thus exhibit g factors very near 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 be due to 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. Electron spin resonance in dpph can be shown with the sample held in a small coil and placed in a uniform magnetic eld. Consider the coils impedance at a frequency . The presence of the resonance r = geB/(4m) will show itself at = r when energy will go into changing the state of the electrons from one value of ms to the other. At resonance there will be a minute decrease in the Q or quality factor of the coil. This decrease can be picked up by connecting the coil (inductance L) to a capacitor C together with other components to make a resonant circuit. When set up to oscillate weakly at a frequency (= 1/(2 ) LC ) it is possible to see the resonance because a tiny decrease in Q can be easily detected by amplifying electronics. Sweeping through the resonance is best done by changing B since it is electronic more difcult to sweep through with frequency and maintain exactly the same amplitude of oscillations. In our case, the eld is produced

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by a Helmholtz coil (see Section 3.3 and page 79 of the bench manual for further explanations of Helmholtz coils).

3 The apparatus
The manual about the spectrometer that you will be using is on the bench and also has been placed as a PDF le (named CWS 12 50 manual) on the computer. The pages relevant to the ESR experiment are pages 19, 25 - 41, 55, 71 - 72, 79, 82. Figure 15-2 shows a schematic diagram of the ESR spectrometer.

Fig. 15-2 : Schematic diagram of the electron spin resonance experiment

Note that this diagram, as well as the bench manual, also refer to NMR (nuclear magnetic resoance). Although this apparatus can be used for this type of experiment, we will only use it for electron spin resonance (ESR). Consequently, the reference in Fig. 15-2 (and bench manual) to the electromagnet

E LECTRON S PIN R ESONANCE and NMR are not relevant to this experiment.

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The sample is placed in a coil that is in parallel with a capacitor. This is the resonant circuit (also called a tank circuit) and oscillates at 50 MHz. The phase-locked loop (PLL) is a circuit that ensures this resonant circuit oscillates at the frequency that we set (using the computer). So the value of the capacitance is changed until the circuit is locked onto the required frequency. This variable capacitor is NOT the classical metal plate type (which would be inconvenient to change electronically). An component called a varactor diode acts like a variable capacitor that can be changed by adjusting the applied voltage to it.

3.1 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 switching the amplitude of the applied magnetic eld from high to low values in a sinusoidal manner (modulation) at 38 Hz and detecting the difference between them. Moreover, the 50 MHz frequency is ltered on the detection side of the electronics and only the signal amplitude difference (due to modulation) 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 obtain. A Lorentzian line prole is expected for the absorption when signal amplitude is plotted (on the y-axis) against the magnetic eld (x-axis) as shown in Fig. 15-3.
1.0 0.8 0.6 0.4 0.2 0.0 -10 -5 0 5 10

Signal Amplitude (arbitrary units)

Magnetic field (Gauss)

Fig. 15-3 : The Lorentzian line shape of an absorption (resonance) line.

The detected signal is a differential of the Lorentzian line shape as given in Fig. 15-4. Differential detection enables the precise value of the absorption peak height position to be determined since it corresponds to the point where the differential signal equals zero (the zero-crossing). Moreover, the line width of the Lorentzian can easily be obtain since it is the horizontal distance between the peaks (positive and negative going peaks) in the differential 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, or with EXCEL if you are very familiar with it.

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1.00 Differential signal amplitude (arb. units) 0.75 0.50 0.25 0.00 -0.25 -0.50 -0.75 -1.00

S ENIOR P HYSICS L ABORATORY

-10

-5

10

Magnetic Field (Gauss)

Fig. 15-4 : The differential of the absorption signal shown in Fig. 15-3. The is the signal that is received from the spectrometer.

3.2 Signicance of line-width

The 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 a great probe of the electronic or nuclear magnetic environment. The line becomes broader with increasing coupling of the electrons to their environment.

3.3 Helmholtz coil

The magnetic eld is supplied by the Helmholtz coils shown schematically in Fig. 15-5. 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 by this experiment) a difculty arises because all magnetic materials have a remanent eld: a nite eld is produced even when the magnetising current is zero. This makes the setting of reproducible elds difcult: AC demagnetization is needed between current changes. 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 nite region at the centre of the conguration.

3.4 Dip circle

The dip circle, shown in Fig. 15-6, 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. 15-5 : Helmholtz coils, where the radius of each coil is equal to the distance of separation. Note the magnetic eld in the centre is particularly uniform. (from The Physics of Electricity and Magnetism, W.T. Scott (Wiley, 1962))

4 Experimental Procedure
Make sure that the spectrometer is connected as shown on page 19 of the bench manual. Make sure the dpph sample is inserted in the Probehead as shown on page 19 of the bench manual. Make sure that the Helmholtz coil and Probehead combination are standing on the Perspex sheet. You will need to rotate the Helmholtz coil/Probehead assembly horizontally later and the perspex makes this easier.

4.1 Becoming familiar with the spectrometer software

Start the CWNE software. 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. Click on single (for a single scan) and let Acc be 1 (for one scan) in the bottom right hand corner of the screen - in the Acquisition section. Click on the Start button in the Acquisition section in the bottom right hand corner. This will start the scan. You should obtain a differential scan as described in section 3.1 If the spectrum does not ll the full vertical scale (or close enough to it) then increase the Gain in the Detection panel located at the bottom left hand side of the screen.

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Fig. 15-6 : The dip circle gives the angle of the Earths magnetic eld.

If the horizontal scale is too small or too large, then you can change this by changing the Field Sweep value. Note that if the range becomes too large you might lose horizontal resolution. The noise in the signal can be reduced with increasing number of accumulations. To do this, increase the number next to Acc in the bottom right hand side of the screen. You must also depress the Acc button on the top left hand side of the screen. You can also vary the 2nd Mod Amplit and Sweep Time to try and obtain as narrow a signal as possible while maintaining a good signal. After you have obtained a spectrum with which you are happy, then you can save it from the File menu on the top left hand corner of the screen. The le will be saved with a .dcw extension. This spectrum can be processed by clicking on the Proc button on the top left hand side of the screen. This will take you to another screen with top and bottom graph panels. Click on the Open File button to load the le you have just saved. This will load in the top panel. Click on the 1st Derivative button on the top left hand side of the screen to load this into the bottom panel. This will now enable you to do measurements on this spectrum. Click on the VE button, located on the left hand side below the top panel, to normalize the spectrum to the panel in the vertical direction. Click on the G button, located on the left hand side below the top panel, to calculated the g-value, which will be displayed on the bottom right hand side of the screen. To obtain the line width of the 1st derivative click on the SDB button. This is distance between line maximum and minimum. Click on the Absorption button (top left hand side of the screen) to display the absorption line prole. The program does this by integrating the 1st derivative line.

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Click on the HDB button (under the top panel) to display the full width at half maximum height of the line. This number is displayed in the bottom right hand side of the screen. You can also obtain a number that is proportional to the number of electrons in the sample by clicking on the Integral button (below the top panel) You can save the 1st derivative data so that you can read it into ORIGIN or EXCEL by clicking on the Export ASCII button located at the top left hand side of the screen. The default le name is txt. This le can be imported into ORIGIN with the File > Import > Single ASCII menu.

C1

Get the demonstrator to check that you are able to obtain a reasonable signal and be able to load it into ORIGIN or excel.

4.2 Measurement of the Earths Magnetic Field

The Geographic North Pole is actually a magnetic South Pole as shown in Fig. 15-7

Fig. 15-7 : Geographic north and south poles are actually magnetic south and north poles, respectively. Note that the magnetic eld like emerge at an angle with respect to the Earths surface for Sydney.

Use the dip circle to determine the angle of the Earth Magnetic eld. You will need this later when determining the magnitude of this eld. Keep the compass away from iron objects since this will distort the direction of the eld.

4.3 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 the g-value by obtaining the resonant frequency and using the equations given in the introduction. However, the Earths eld will add or subtract from the applied eld in the Helmholtz coil depending on the

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orientation of the axis of symmetry of the coil with respect to the horizontal components of the Earths eld, which must be taken into account. 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. This is the resultant eld that will be applied to the electron. However, the horizontal component of the Earths eld will subtract from the applied eld if these two elds are antiparallel. 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. Use the angle determined from the dip circle to determine magnitude of the Earths magnetic eld. Outline your method in your logbook.

C2

Get a demonstrators to check before proceeding.

4.3.1 Results and Analysis Save your results and analyse using ORIGIN (easier) or EXCEL (harder), include errors in your analysis. Remember, there is the accumulate feature in the program that will enable you to accumulate many scans in order to reduce any noise. Also determine the line width in your analysis. Compare the line width of DPPH with TCNQ and determine which sample has electrons with stronger coupling to their environment. Write a conclusion.

C3

Get a demonstrator to check before proceeding.