SPS 4110: Senior Laboratory Experiment P-2 Electron Spin Resonance

By: Guinevere Shaw Department of Physics & Space Sciences Florida Institute of Technology email: gshaw2008@my.t.edu Partner: Nick Deschenes Date: April 12, 2012

ABSTRACT
Electron spin resonance (ESR) is a useful tool for investigating the energy absorption spectra of many materials with unpaired electrons (paramagnetic materials). In this lab exercise you will explore the absorption of a paramagnetic molecule. A paramagnetic material has an electronic structure that leaves an electron in a state such that it does not have a partner of opposite spin. This implies that the molecule will have an intrinsic magnetic dipole moment. This experiment will allow you to verify the quantum mechanical model used to describe the paramagnetic system. You will be able to observe the absorption behavior of the electron, as well as determine the Land g factor associated with this system. In conclusion g = 2.0 and the graph of the frequency versus the magnetic

1.

Objectives

How can we measure the Land g factor for the free electron in DPPH as predicted by quantum mechanics and then graph the frequency against the magnetic eld. 2. Theory

of its intrinsic spin. Since the spin of an electron may either be up or down, so may its magnetic moment. This implies that, in the presence of an external magnetic eld, one spin state will be higher in energy than the other. More specically, the spin with a moment pointing in the direction of the external eld is lowest in energy. These states have an energy E, as either

ESR is a purely quantum mechanical eect. It relates the interaction of an external magnetic eld to an electrons magnetic moment, which is a result

1 E = gB B. 2 1

(1)

Where g is the Lande factor, B is the Bohr magneton (a constant), and B is the value of the external magnetic eld. Thus, the change in energy from the negative to the positive spin state can be written Figure 1. Sketch of the structure of a DPPH molecule showing the nitrogen (N) contributing the free electron. Below is an image of what the experiment setup resembled.

E = gB B.

(2)

Where E is the energy of an RF photon, h is Planks constant, and is the frequency of the photon. When a photon of energy E is incident on an electron in a eld of strength B electron resonance will be observed.

E = h 3. 3.1. Equipment Materials and Equipment

(3)

1. ERS Basic Unit 2. Pair of Helmholts Coils (r = 6.8cm) 3. Three Saddle Bases 4. Two-channel oscilliscope 5. ESR Adapter 6. Measuring Resistor 1 7. D.C. Power Supply, regulated 8. Variable Low-voltage Transformer SE 9. Voltmeter, Ammeter 4. Experiemnt Figure 2. Experiment Setup The next steps is to increase the frequency, f, of the HF oscilliscope so that the resonance line moves toward the right of the oscilliscope screen. This is because resonance now occurs with a stronger magnetic eld density, B. Then bring the resonance line back to its original position by increasing the static magnetic eld. My partner and I measured the frequency, f, and the d.c. current, I, which is proportional to B. To measure I exactly, reduce the ESR signal as for as possible by decreasing the amplitude modulation and then align the remaining ESR signal with the static eld symmetrically about the middle of the screen.

The electrons that my partner and I will manipulate are located in the paramagnetic molecule Diphenyl-Picryl-Hydrazyl (DPPH). DPPH is pictured below; notice the unpaired electron. This electron is also very weakly bound to the nitrogen atom. The combination of these two properties makes this molecule ideal for studying the magnetic properties of the electron. The DPPH has been loaded onto a piece of cotton and placed inside of a sample tube. The sample tube should then be placed in a coil and inserted into the mount (light grey cylinder in Figure 2). Consult the manufacturers manual for any necessary information concerning the setup of this device. 2

Figure 3. Oscilliscope image of ESR signal.

My partner and I then measured multiple points by rst adjusting the frequency and then the current. Below is a chart of corresponding points.

A seen in the image below

Figure 5. Describes the oscilliscope waves and how to measure each eld. From the beginning using equation (3) we nd that h also equals:

Figure 4. Frequency and Voltage, voltage used to determine current. The Flux density B for the almost homogeneous magnetic eld of the pair of Helmholtz coils can be easily calculated for a known current I. If the number of turns on each coil is n and the distance between the coils is the same as the radius of the coil, r, then it follows from Biot and Savarts Law

h = ge B B This equation follows:

(6)

ge B = B h

(7)

Where... h = 6.625*1034 W s2 (P lanck sConstant) B = 9.273*1034 Am2 (BohrM agneton) Finally the g-factor can be found by using the gradient of the curve of B .

4 3 n B = o ( ) 2 I 5 r The magnetic eld is constant:

(4)

ge = o = 1.2566 106 n = 320 rad r = 6.8 cm Vs Am

h B B

(8)

So now B is equal to:

The result is that the resonant frequency is proportional to the resonant magnetic ux density, B. Using the proportional constant B , the g-factor has a value of about 2.0. Below is a chart of all the g values found using the above equations. Also we plotted the resonant frequency, , as a function of the resonant ux density, B. Which is proportional to the current, I, through the Helmholtz coils.

B I = 4.23 mT A

(5)

To nd the error in this equation we derive:

V = .250 .1V R= 1.02 I = .354 I = I( V + R ) = .148 V R I = .354.148 Now that we know the error in the current we can calculate the error in the magnetic eld.

and...

I B = 4.23 A = amps mT A To nd the error in B we multiply the constant by I plus the error.

B = (.354 .148) 4.23 B = 1.497.628 Then to nd the error in the g-factor:

ge = 5. Error

h B B

There was error in both the voltage as well as the frequency because they were both measured experimentally. The voltage was measured using the voltmeter and the frequency was measured using the fequency meter. Since this was measured experimentally there is an error in calculating the current, I, the magnetic ux density, B, and nally the g-factor, ge . Below is an example nding the error in the mentioned equations. The rst equation is the current, I.

B = 1.497 T.179T h = 6.625*1034 W s2 (P lanck sConstant) B = 9.273 1024 Am2 (BohrM agneton) = 41486000Hz 1Hz The error in the g-factor:

ge = ge (

h B )( + ) = 5.900 10 59 o B

(9)

Below is a chart showing what they error is when you plot versus B.

I=

2V R R = 1 4

6.

Conclusion

In this lab my partner and I learned about electron spin resonance. The application and experimental setup was dicult at rst but once we adjusted the oscillscope setting we were able to produce the correct signal for the magnetic eld and the current. Finally in this lab, it was the rst time that I personally did the calculations, with measured points, and the results were correct. The nal ge is theoretically 2.0 and my measured value is 1.98 which is good.