ELECTRON SPIN RESONANCE

Last Revised: July 2007 QUESTION TO BE INVESTIGATED How can we measure the Land g factor for the free electron in DPPH as redicted !y "uantum mechanics# INTRODUCTION $lectron s in resonance %$&R' is a useful tool for investigating the energy a!sor tion s ectra of many materials with un aired electrons % aramagnetic materials'( )n this la! e*ercise you will e* lore the a!sor tion of a aramagnetic molecule( + aramagnetic material has an electronic structure that leaves an electron in a state such that it does not have a artner of o osite s in( ,his im lies that the molecule will have an intrinsic magnetic di ole moment( ,his e* eriment will allow you to verify the "uantum mechanical model used to descri!e the aramagnetic system( -ou will !e a!le to o!serve the a!sor tion !ehavior of the electron. as well as determine the Land g factor associated with this system( THEORY $&R is a urely "uantum mechanical effect( )t relates the interaction of an e*ternal magnetic field to an electron/s magnetic moment. which is a result of its intrinsic s in( &ince the s in of an electron may either !e u or down. so may its magnetic moment( ,his im lies that. in the resence of an e*ternal magnetic field. one s in state will !e higher in energy than the other( 0ore s ecifically. the s in with a moment either ointing in the direction of the e*ternal field is lowest in energy( ,hese states have an energy E. as

%1'

2here g is the Lande/ factor. 3 is the 3ohr magneton %a constant'. and B is the value of the e*ternal magnetic field( ,hus. the change in energy from the negative to the ositive s in state can !e written %2' ,herefore. !ecause g and 3 are constants. there are airs of values of

the energy E and of the e*ternal field B that satisfy $"( %2' and result in a transition of s in states( +t commonly attaina!le magnetic field strengths the corres onding energy lies in the radio4fre"uency %R5' regime( 2here the general e* ression for the energy of a hoton a lies %6' 2here E is the energy of an R5 the fre"uency of the hoton( 2hen a hoton. h is Plan7/s constant. and is hoton of energy E is incident on an

electron in a field of strength B electron resonance will !e o!served( EXPERIMENT ,he electrons that you will mani ulate are located in the aramagnetic molecule Di henyl4Picryl4Hydra8yl %DPPH'( the un aired electron( nitrogen atom( DPPH is ictured !elow9 notice ro erties ma7es this laced inside of ,his electron is also very wea7ly !ound to the

,he com!ination of these two

molecule ideal for studying the magnetic ro erties of the electron( ,he DPPH has !een loaded onto a iece of cotton and a sam le tu!e( ,he sam le tu!e should then !e laced in a coil and inserted into the mount %light grey cylinder in 5igure 2'( :onsult the manufacturer/s manual for any necessary information concerning the setu of this device(

Figure 1. Sketch of the structure of a DPPH molecule showing the nitrogen (N) contributing the free electron.

5igure 2 shows a !loc7 diagram de icting the e* erimental setu ( ,here are essentially two circuits: ,he first controls and monitors the R5 signal driving of the electrons %at left'. and the second controls the e*ternal magnetic field %right'( -ou should o!serve the out ut of the a!sor tion of the DPPH on one channel of the oscillosco e %D: cou le the o4sco e channel' and the voltage across the resistor on the other channel( ,he fre"uency of

12 V - G + 4=> R5 5re"( @A, %3?:' T Amp R~1;< )? Ch1 Ch2

12 V + G -

Figure . ! "rawing of the basic elements of the e#$eriment is shown. %he circuit is also shown. the R5 in ut can !e selected !y a 7no! located on the to of the sam le4

mount !o*( ,his !o* also contains a !ridge circuit to am lify the a!sor tion signal and cancel out the electronics resonance effects( ,he second circuit controls the current running through the Helmholt8 coils. and conse"uently the e*ternal magnetic field( + s ecial voltage source is to !e used which a lies a ram ed signal with a long eriod( ,his signal is one4half of a triangle wave. whose fre"uency. sign. and am litude you may adBust( -ou should o!serve the half triangle on the remaining oscillosco e channel !y monitoring the voltage dro across the 1C resistor in this circuit %see 5igure 2'( Observing t ese t!" sign#$s !i$$ #$$"! %"& t" '"rre$#te t e "''&rren'e "( res"n#n'e t" t e v#$&e "( t e e)tern#$ B (ie$*+ ,he ur ose of the resistor is to limit the current in the circuit and allow you to o!serve the signal on the oscillosco e( + measurement of the resistor/s value and the oscillosco e trace will allow you to calculate the current in the coils at any given time( +s the voltage increases from the triangular current source so does the current running through the coils. which in turn creates the desired magnetic field around the sam le( +t a s ecific value of this field %see $"( 2' in the out ut of the resonance will occur and you will see a very o!vious di

R5 device( -ou will see two symmetrical di s. one as the 3 field ram s u through the value s ecified !y $"( 2 and another as it descends through this same value( ,hese di s occur !ecause the electrons are a!sor!ing some of the hotons( )f you ram the field too "uic7ly the ea7s will not !e symmetric( :an you e* lain why this ha ram ing the ram s( )t may ta7e some ens# :hoose a re etition rate and

eriod such that the entire sha e of the resonance is seen during ractice to achieve the right sha e and

re etition rate for the ram ( + uniform magnetic field can !e reasona!ly achieved using Helmholt8 coils( Helmholt8 coils are com osed of two coa*ial coils of wire se arated !y a distance e"ual to their radii( + derivation of the field from two coils in the Helmholt8 configuration is in the + endi*( $ach coil should have the same num!er of windings and the same radius( ,he coils should also have the

same current running through them %wired in series. 5igure 2'( 2hen all of these conditions are met there will !e a volume of nearly uniform field within the coils( Ase the =aussmeter to resonance of the sam le/s electrons# +t this time you should ause and !ecome more familiar with the rovided on the course oscillosco e/s functions9 the manual has !een rove that the field is uniform over the length of the sam le( How do you thin7 variations in the field will effect the

we!site( )n addition to the normal voltage and time range adBustments. you will need to understand how to e* ort data to an e*ternal dis7( ,a7e resonance data for at least D different fre"uencies of R5 radiation( -ou may wish to utili8e the oscillosco es averaging function in order to reduce noise( 0agnetic 5ield :ali!ration: ,o use $"( %2' you will need to 7now the value of the magnetic field where a!sor tion occurs( ,his may !e accom lished !y using a =aussmeter( + =aussmeter is a long thin ro!e that measures the value of a magnetic lace the ro!e inside the coils( -ou can field via the Hall $ffect %which you may e* lore in another e* eriment'( Remove the DPPH sam le and o!serve the =aussmeter/s read4out on the oscillosco e while simultaneously watching the triangle wave on another channel( ,his will allow you to create an e* ression for B as a function of time. or to sim ly correlate individual values to true magnetic field strengths( -ou must also measure the uniformity of the magnetic field( Remove the sam le and measure the field in a hori8ontal line starting 2cm !ehind the center of the coils to 2cm in front of the coils in 2mm ste s( Do the same for a vertical line starting 1 cm !elow the center and ending 1cm a!ove the center in ste s of 2mm( 5rom each of the data sets. fit a smooth curve to the field vs( osition( 0easure the si8e of the sam le( Asing the fit curve. average the field over the length of the sam le( Re eat for the vertical thic7ness of the sam le( Do not include the glass thic7ness in your averages(

Divide the results !y the field at the center of the target( ,hese will !e correction factors that you will need to use in calculating g( Resonance Data +nalysis: ,o get the value of the field at resonance ta7e your recorded data and fit a gaussian lus !ac7ground to your ea7( 5it only the voltage values in ea7 sha e as it is not ro*imate the vicinity of the ea7( Do not try to fit the full

gaussian( ,he centroid of the gaussian is the time at which the resonance was ma*imum( Ase the chis"uare of the fit to determine the a uncertainty in the osition of the centroid( Ase your fre"uencies and the measured field of each resonance to calculate the Lande/ g factor and its error( Re ort: -ou should re ort: ,he value of the resistor ,he field vs( current cali!ration fit % lot re"uired' ,he field vs( distance curve and fits % lot re"uired' ,he correction factors + fit of resonance curve you used to arrive at a value for the magnet current % lot re"uired' ,he value of the Lande/ g factor %nominal E 2(006F' for this system and its error( ,he variation in the magnetic field over the area of the DPPH sam le( +s you have seen. the a!sor tion a ears as symmetrical di s in an 2e have seen the henomenon has

otherwise constant signal( However. anomalous !ehavior has !een o!served when the fre"uency of the 3 field source is very low( signal develo a s i7e trailing the ty ical a!sor tion waveform. which is of

much higher magnitude than the standard !aseline( ,his

not !een fully investigated. !ut a system(

ears to !e intrinsic to this

articular

,here are several theories(

@ne identifies the cul rit as an ly( +nother theory is that there

unwanted !ehavior of the current ower su

are resonances in the sam le mount that were not corrected for at lower fre"uencies of the 3 field current( -ou should investigate this !ehavior. as it is an e*cellent e*am le of the fact that all e* erimental setu s have limitations and !ehaviors that deviate from theory( Determine the ma*imum field at which this !ehavior occurs and ma7e sure that your field values are a!ove this( Re ort the ma*imum current where this effect is seen( Provide a treatment of this issue in your discussion(

endi*: Helmholt8 Derivation air of Helmholt8 coils( 2e !egin with the e* ression for

2e wish to derive an e* ression for the strength of the magnetic field B along the a*is of a

the magnetic field of a single loo %from the 3iot4&avart Law':

along the a*is running through the loo

where 0 is the ermea!ility of the vacuum. I is the current through the loo . R is the radius of the coil. and x is any coordinate along the a*is of the two coils( However. our Helmholt8 coils are not single coils. !ut consist of n num!er of single turns. thus yielding:

2e will lace our sam le halfway in!etween the two coils( ,his sets x to R/2. !ecause Helmholt8 coils are se arated !y a distance e"ual to their radius( ,his su!stitution yields:

!lso& there are two coils so we must "ouble our e#$ression'

%hus& our $owers of algebra ha(e le" us to a useful result'

$*tension: )f I = I(t) then you may also may achieve B(I,R,t)(