EPR SPECTROSCOPY
Factors affecting of “A” and “g” value
No. of signals in EPR with fine splitting
EPR Spectrum of Transition Metal Complexes
FACTORS AFFECTING OF “G” VALUE
• g stands for Lande splitting factor or spectroscopic splitting factor.
• The value of g is not constant but it is a tensor quantity. For a free electron its value is 2.0023 but this value
is slightly modified for electrons in molecules.
• Virtually all free radicals and some ionic crystals have almost same value of g as for free electrons, but this
value is modified by ± 0.03
• In some ionic crystals, the values of g vary from 0.2 to 0.8
• The value of g depends upon the orientation of molecule having the unpaired electron with respect to
applied magnetic field
• In the case of a gas or solution, the molecules have free motion and value of g is an averaged over all
orientation. But in the case of crystals, the movement of electrons is not free.
• However, in the case of paramagnetic ion or radical situated in a perfectly cubic crystal, the value of g is
same in all directions, i.e., the value of g does not depend upon the orientation of the crystal.
• On the other hand the value of paramagnetic ion or radical situated in a
crystal of low geometry depends upon the orientation of the crystal.
• There are three axes in crystal. The values of long x, y, and z axes are
denoted by gx, gy and gz respectively. In the case of tetragonal site, the
values of gx, gy are equal to referred to as g perpendicular. This value is
generally attained when external magnetic field is perpendicular to z-axis.
The value of gz is obtained when the magnetic field parallel to z-axis. The
value of gz is denoted by g is parallel
• Spin orbit coupling
• Electronic structure and bonding
• Oxidation state of metal
• Zero field splitting
• Crystal field and ligand field effect
FACTORS AFFECTING OF “A” VALUE
• The spectrum between the hyperfine splitting of two absorption lines gives the
hyperfine splitting constant A, which is measure the electro nucleus interaction
• An Anisotropic effect
• Ratio of the nuclear magnetic moment of the nuclear spin
• Electron spin density in the vicinity of nucleus. This is Fermi contact term which is
measure the probability of bonding pair electron existing at both nuclei
a) When single electron interact with one nuclei the no. of splitting pattern weill be
equal to (2I1)
b) When an electron interact with the n equivalent of nuclei, the splitting is split
into (2nI1) gives a multiplet
ZER0 FIELD SPLITTING OF D2
ZERO FIELD SPLITTING OF D3
EPR SPECTRUM OF TRANSITION METAL
COMPLEXES
• EPR spectra of transition metal complexes is complicated because •
Theyhave several degenerate orbitals and unpaired electrons.
• There is anisotropy in g-factors.
• There exist zero field splitting.
• In a complex the orbitals do not interact equally with ligands and the energy
levels are split into two or more groups.
For example, in a octahedral complex there are 3t2g lower levels and two eg
upper levels
EPR SPECTRUM OF TRANSITION METAL
COMPLEXES
• For octahedral first row transition metal complexes, the crystal field energy is greater
than the spin orbit interaction energy.
• For understanding the EPR spectrum the following points must be considered.
• Number of d-electrons in the metal.
• To identify whether it is a low spin or high spin complex.
• Effectof Jahn-teller distortion.
• Zero field splitting and Kramer’s degeneracy.
• For heavier atoms due to zero field splitting it is difficult to observe and interpret the
EPR spectrum. For example, second and third row transition metal complexes
EPR SPECTRUM OF D1 OR VO(II)
• VO(IV) Complex –d1 system
• In an octahedral field, the ground state is t2g and in tetrahedral field, the
ground state is eg. There is a large spin-orbit coupling which leads to a short
spin relaxation time for the electron and will results in broad absorption lines.
Therefore the complexes are studied at liquid helium temperature.
• For example, • The EPR spectrum of [VO(glycolate)2]2- in water (V, I=7/2)
shows eight equispaced lines, since the system is isotropic. There is only one
g value
For vanadyl complex of d,l-tartrate at room temperature, two sets of spectral lines are observed.
One with g11>ge and another with g1l<ge
EPR SPECTRUM OF MANGANESE(II) OR D5
• It is d5 system and it have 5 unpaired in high spin whereas 1 unpaired
electron in low spin.
• I = 5/2 for Mn 2+
• Hyperfine Splitting (2nI+1) = (2(1)(5/2)+1) = 6 lines
• Eg : [Mn(H2O)]2+ , [Mn(CN)]2- ,
• Superhyperfine splitting = 6(5) = 30 lines
EPR SPECTRUM OF COBALT(II) OR D7
• It is d7 system and it have 3 unpaired in high spin whereas 1 unpaired
electron in low spin.
• I = 7/2 for Co 2+
• Hyperfine Splitting (2nI+1) = (2(1)(7/2)+1) = 8 lines
• Eg :Co3(CO)9Se, [CoF6]4-, Co3(CO)9Rh
EPR SPECTRA OF CO3(CO)9SE AND
CO3(CO)9RH
• Hyperfine Splitting of Co3(CO)9Se (2n+1) = (2(3)(7/2)+1) = 22 lines
• Hyperfine Splitting of Co3(CO)9Rh
(2nI+1) (2nI+1) = 22(2) = 44 lines
EPR SPECTRUM OF NICKEL(II) OR D8
• Ni(II) has A2g ground state in an octahedral field. Spin-orbit coupling leads to
greater g value than that for a free electron and splits A2g configuration. This
is because of the zero field splitting and it is very anisotropic. Therefore EPR
spectra of Ni(II) octahedral complexes are difficult to detect.
• TheNi(II) square planar complexes are diamagnetic in nature. Therefore EPR
spectra are not recorded for them. They are used to dilute the spins of
copper (II) complexe
EPR SPECTRUM OF IRON FE(II) 0R D6
• Low spin complex of Iron is EPR Inactive where as high spin Iron is EPR active
• I = 2 fot Fe(2+)
• Hyperfine splitting is (2nI+1) = (2(1)(2)+1) = 5 lines
• Eg : [Fe(OH2)6]2+,Deoxy Hb
EPR SPECTRUM OF COPPER(II) OR D9
• I = 3/2 for Cu 2+
• Hyperfine Splitting (2nI+1) = (2(1)(3/2)+1) = 4 lines
• Eg : [CuCl4]2-, Bis salicylaldiminecopper(II) complex, [Cu(bpy)3]2+
The ground state of an octahedral d9 system is Eg. Since there is large Jahn-Teller distortion, the
spectrum is recorded at room temperature