CYN-525

Advanced Molecular
Spectroscopy
Lecture 25

Dr. Pavan Kumar

Systems with more than 1 unpaired electron

Electron-exchange interactions

The singlet and triplet states are split apart in energy

by the electron-exchange interaction

Electron-electron spin interaction – Fine interactions

Systems with more than 1 unpaired electron

When anisotropic magnetic dipole-dipole interactions are

taken into account then three fold degeneracy is removed
even in zero magnetic field – Zero field splitting

ZFS – is primarily attributed to dipole-dipole interactions in

organic molecules and Spin-orbit coupling in transition
metal ions

ZFS can reach values of hundreds of GHz and make the

spectra broad / weak

Number of electronic spin states – 2S+1

Zero field Splitting
Zero field Splitting

Transition metal ions (TMI) the – ZFS is mainly due to spin-orbit coupling

TMI with even or odd number of unpaired electrons – integer or half integer spins

Systems having odd number of unpaired electrons must always have a two-fold degenerate electron spin state in zero field

Kramers theorem

These ms = +/- ½ states are called Kramers doublets

The EPR transition from -1/2 to +1/2 is detectable around the g = 2 resonance at any EPR spectrometer frequency

Metal ions with half integer spins are called Kramer ions

D and E values provide a means for deviation from spherical and axial symmetry for the two electron wavefunction
Zero field Splitting

SOC can occur in d1 systems also – leading to ‘g’ anisotropy

Zero field Splitting
Zero field Splitting
ENDOR spectra
Electron Nuclear Double Resonance

The ENDOR signal is the difference between the intensity of the

EPR line with and without - the RF driving one of the two NMR
transitions
ENDOR spectra

The CW-ENDOR effect heavily depends on the ratio of the

various relaxation times.
For radicals in solution, where often the ENDOR enhancement
is detectable only with a convenient choice of solvent and
temperature.

Resolution in ENDOR scales like NMR – with Magnetic field

One set of nuclei – only two lines in ENDOR

The frequency where the lines occur reveal information

about the nuclei coupling to the electron

Very useful in randomly oriented samples – where hyperfine

splitting constants can be hard to recognize. The EPR
excitation only excites a certain set of molecules with a
narrow band of orientations.

ELDOR – Electron-Electron Double Resonance