Determination of Land g-factor

Introduction
In recent years Magnetic Resonance has developed into a very useful and powerful tool in solid state S research. In this method, magnetic spin ( ), associated with the electron, precess around the applied magnetic field H and degenerate energy levels split into discrete energy levels. When electromagnetic energy is supplied to the electron (sample), the energy will be absorbed by the sample when the energy is equal to the energy difference between the above discrete energy levels. This form of spectroscopy finds many applications in the investigation of spin of the electron, crystal structures, crystal environmental effects, dynamic effects, defects in solids, etc.,.

Elementary Magnetic Resonance

S We know that the intrinsic (spin) angular momentum of the electron (S = +1/2, -1/2) couples with to give a total angular . This coupling gives rise J the orbital angular momentum of the electron L to degeneracy of energy states. These degenerate states will split into discrete energy levels under the applied magnetic field H. The spinning electron possesses a spin magnetic dipole moment s=g B , where g- Land g-factor (g = 1 for pure orbital momentum, = 2 for free electron spin), S B is the Bohr magnetron = eh/4me. Similarly, orbiting electron possesses an orbital magnetic dipole L moment l =g B . If the electron is placed in a magnetic field H , the spin magnetic dipole moment will have the potential energy E= s . H (ignoring spin-orbit interaction). Thus, the magnitude of energy of the electron in a magnetic field H is E=gHS B where S is the spin magnetic moment. Therefore, ignoring spin-orbit interactions, a given energy level of an atomic electron will be split into two levels (one for +1/2 (E +) and other for -1/2 (E-), differing in energy by an amount of E = E+ -- E- = gHB as shown in the following fig.1.

1 g H r B 2

1 g Hr B 2

Hr

Fig.1: Energy splitting of a free electron in a magnetic field and resonance condition for electron spin resonance. 1

If photons of an energy h (electromagnetic radiation) is supplied to the sample (electron) with its direction perpendicular to the magnetic field H, then the sample absorb energy h when it is equal to E = gHrB. This is called resonance condition i.e., h = gHrB. This will induce electron transition from lower state to higher state of energy difference gHB. Thus, at resonance, we get a peak (or dip) due to the absorption of energy by the system (sample).

Experimental Technique
If we consider a free electron and substitute the proper value of constants in the equation: g = 2.00, B = 0.927X10-20 erg/gauss and h = 6.625 X l0-27 erg-sec in resonance condition, we get /Hr = 2.8 MHz/gauss That is ESR can be observed at radio frequencies in a magnetic field of a few gauss or in the microwave region in a magnetic field of a few kilogausses. The latter alternate has many advantages: (a) For each transition the absorbed energy is much larger and thus improved signal-to-noise ratio, high resolution etc. (b) A high magnetic field is used, thus providing separation between levels that are intrinsically wide and would remain partially overlapped at low fields. Because of these advantages, ESR in microwave region is preferred for research purpose, though it is very sophisticated and expensive. The former one is preferable, if the basic understanding of the subject is the main criteria as is usually the requirement of class room experiments, the observation of ESR in low magnetic field and in a radio frequency region makes it a lot simple, inexpensive and within the reach of every graduate laboratory. In the radio-frequency region, two types of methods are chiefly used: (i) The method of reaction on the generator (ii) The method based on a determination of the change in a load factor of the oscillatory circuit due to paramagnetic loss. The latter method has been used here. The sample under investigation is placed in an induction coil, which is the component of the tank circuit of the oscillator (frequency generator). It is based on the fact that under certain conditions such as absorption of power from generator, the watt load (w) on the generator changes. To make the detection simple and more sensitive, the magnetic field is modulated with a low frequency field 50 Hz in the present set-up.

Description of the ESR Spectrometer Basic Circuit

A block diagram of the ESR Spectrometer is given below in Fig. 2, and a brief description follows.

Fig.2: block diagram of the ESR setup. The first stage of the ESR circuit consists of a critically adjusted (marginal) radio frequency oscillator having a frequency range of approximately MHz. This type of oscillator is required here, so that the slightest increase in its load decreases the amplitude of oscillation to an appreciable extent. The sample is kept inside the tank coil of the oscillator, which in turn, is placed in the 50 Hz magnetic field, generated by the Helmholtz coils. At resonance, the oscillator amplitude registers a dip due to the absorption of power by the sample. This obviously, occurs periodically four times in each complete cycle of the Helmholtz coils supply voltage. The result is an amplitude modulated carrier which is then detected using a FET demodulator and amplified by an op-amp circuit. Highly stabilised and almost ripple free power supply for the above circuit is obtained using an integrated circuit (IC) regulator.

Phase Shifter
This can compensate the undermined phase difference which may be introduced in the amplification stages of the spectrometer and oscilloscope.

50Hz Sweep Unit

A 50Hz current flows through Helmholtz coils which provides a low frequency magnetic field to the sample. As the resonance is observed at few gausses only, no static magnetic field is applied.

Fig.3: Experimental setup (top) and peaks in CRO (below).

Operating procedure:
1. Switch on H-coil power and adjust the current at ~150 mA. 2. Set the front panel controls of ESR spectrometer as follows Frequency: ~13.3 MHz 3. Observe four peaks on the screen of CRO. 4. Adjust the Phase knob to coincide the two peaks with the other two as far as possible. 5. Adjust the RF-frequency of the spectrometer, current through the Helmholtz coils and sensitivity of X- and Y- channels of the CRO to obtain the best results, i.e., sharp peaks and 4

good signal-to-noise ratio. 6. The observed peaks are in fact absorption dips, because the sample absorbs power from the induction coil. The reason for getting peaks is due to odd number of amplifying stages in the circuitry. 7. Adjust the orientation of Helmholtz coils w.r.t the main unit for best overlap of base lines. 8. If the X-plate signal (50 Hz, from Helmholtz coils) and Y-plate signal (ESR output, from RFoscillator) are in phase, the first and third peaks and second and fourth peaks will coincide. 9. The coincidence of peaks on x-scale needs to be calibrated for magnetic field measurements. The coincidence ensures that the magnetic field is zero at the centre and has the peak values at the two ends. 10. Complete merger of the peaks on y-scale may not occur due to many reasons such as 50 Hz pick-ups, ripples in the power supply etc., Though every effort has been made to minimize these factors but large amplification (~4000) in the circuitry make them substantial. However, any non-coincidence on the y-scale is immaterial as neither any measurement of the y-scale is involved in the calculation of g-factor nor any measurement is made on it.

Calculations:
1. To calibrate the X-plate of CRO in terms of H: (a) Adjust the X-amplifier (CRO) to obtain the max. deflection (say p division). (b) Read the current flowing through Helmholtz coils and calculate the magnetic field 32 n H rms = I gauss, where n no. of turns in each Helmholtz coil = 500; r the radius 10 125 r of the Helmholtz coil = 7.7 cm; I = Irms current (in A) through the coils (hence H is Hrms). (c) The peak-to-peak field (in CRO screen?) will be 2 2 H rms corresponds to p divisions of the CRO X-plate. The zero field is at the middle point. 2. Measure the positions of the two peaks. These should be at equal distances from the middle 2 2 H rms q gauss. point (say q division). The magnetic field at the resonance is thus H r= p 3. The resonance condition h . Substitute the measured values of H HrB and and universal constants h and B values to get the g-factor. g H r B =h or g=

Repeat the above experiment with different and Hr.

Precautions:
1. High currents (~200 mA) should not be allowed to flow through the Helmholtz coils for an extended

Applications
1. Paramagnetic ions in crystals 2. Ferro- and antiferromagnetic materials 3. Unpaired electron in semi-conductors and organic free radicals

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