EPR Flashcards

1
Q

How are EPR and NMR similar?

A

Both use less energetic photons and must be observed in a magnetic field. Both observe spin transitions.

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2
Q

What are the major differences between EPR and NMR?

A

Microwaves are used in EPR and radiowaves are used in NMR. EPR observes electron spin transitions and NMR observes nuclear spin transitions.

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3
Q

What does EPR measure?

A

The energy difference between the two states of a paramagnet when in a magnetic field.

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4
Q

Is an energy difference between states when the molecule has not been placed in a magnetic field?

A

No

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5
Q

Which has a higher magnetic moment, the unpaired electron spin in EPR or the unpaired nuclear spin in NMR?

A

Electron spin in EPR

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6
Q

What is a paramagnet?

A

An atom or molecule with an unpaired electron spin.

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7
Q

What is the zeeman effect?

A

When in a magnetic field, the magnetic moment of the paramagnet will either align with or against the magnetic field.

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8
Q

What is the highest energy state of a paramagnet?

A

When the paramagnet aligns against the magnetic field.

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9
Q

Describe most paramagnets in the ground state at low temperatures.

A

Aligned with the magnetic field (low energy state)

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10
Q

What is the result of using a bigger magnetic field?

A

More energy is required to make the transition between the two states.

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11
Q

Why are microwaves used in EPR?

A

The energy gap between the two electron spin states corresponds to microwaves in the GHz range.

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12
Q

In EPR, which is kept constant the microwave frequency or the magnetic field?

A

Microwave frequency

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13
Q

When does absorption occur?

A

At the resonance position - where ΔE matches the energy of the microwaves

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14
Q

What is the advantage of scanning the magnetic field rather than scanning the microwave frequency?

A

It is easier to scan the magnetic field. This gives a better signal:noise ratio and gives more control of the system.

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15
Q

At what frequency is the field modulation in EPR?

A

100 kHz for measurements at X band microwave frequency

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16
Q

What is the advantage of field modulation?

A

Gives better signal:noise, overcomes wide EPR signals by giving the first derivative graph.

17
Q

What does the zero point on the first derivative graph?

A

The absorption peak when there is no field modulation.

18
Q

How do most EPR instruments generate microwaves?

A

Using a gun diode

19
Q

Where is the sample loaded?

A

In the resonant cavity between the two magnets

20
Q

How are microwaves guided through the EPR instrument?

A

Using waveguides - open air, brass rectangular channels with dimensions corresponding to the X band wavelength (3cm)

21
Q

Why is liquid helium used?

A

To keep samples cool and to allow slower relaxation of the sample.

22
Q

What is the purpose of the circulator?

A

Directs generated microwaves from the microwave source to the resonant cavity and directs reflected radiation to the detector.

23
Q

When is it particularly important to use liquid helium and why?

A

When studying metalloproteins as the excited state of a metalloprotein relaxes very quickly, giving broad peaks.

24
Q

Describe X band microwave radiation.

A

Microwaves resonating at a wavelength of 3cm and a frequency of 9.4 GHz.

25
Q

What happens if the frequency of microwave radiation is increased?

A

Resonance will be seen at higher resolution but this requires a stronger magnetic field.

26
Q

What are the sources of unpaired electrons in biology?

A

Transition metals, free radicals and triplet states.

27
Q

What is a triplet state?

A

An atom or molecule with two unpaired electrons.

28
Q

How can integer spin be detected in EPR?

A

Using parallel mode EPR - where the modulating field is parallel to the applied magnetic field

29
Q

Describe the spectra given by radicals.

A

Sharp, defined features with narrow bands. Tend to have spin 1/2 and are found around g=2.002

30
Q

Can radicals be detected at room temperature?

A

Yes, as they are slow relaxing.