EPR Spectroscopy

Electron Paramagnetic •The electron spin equivalent of NMR

Resonance (EPR) Spectroscopy •Requires unpaired electrons (S ≥ ½)

•information on the environment of the unpaired

p electron → electronic structure,,
geometric structure, physical properties, reactivity, dynamics, etc.
(a.k.a. ESR, EMR)
•EPR transition = flipping the electron spin. E.g. for S = ½…

E ms = +1/2 (↑)
Lecture I. Basic principles of
EPR spectroscopy ∆ms = ±1

ms = -1/2 (↓)
Eric McInnes & David Collison, EPSRC UK National EPR Facility & Service
Photon Science Institute, The University of Manchester
eric.mcinnes@manchester.ac.uk david.collison@manchester.ac.uk H / Gauss (G)

Basics of the experiment The resonance condition

•Fixed frequency, magnetic field swept
E = msgβeH
Microwave bridge waveguide
–back-to-front! Disadvantage. +gβeH/2
(source + detector)
E
ms = +1/2 (↑)
E
N S hν = gβ e H
xxxx

xxxx

Electromagnet
Zeeman
hν
modulation Cavity or g=
coils resonator ms = -1/2 (↓)
-gβeH/2
β e H res
•Detected as 1st derivative of absorption signal ν (GHz)
-Zeeman modulation = 714.5
Absorption H res (G)
1st derivative Hres h = Planck’s constant
= 6.6261x10-34 J s
H βe = Bohr magneton
= 9.2740x10-24 J T-1
= 4.6686x10-5 cm-1G-1

H/G

1
 Frequency vs. Field
•Microwaves appropriate for convenient lab magnets
•Can use different fixed frequencies.
Electron Paramagnetic
•Advantages to both up- and down-frequency/field Resonance (EPR) Spectroscopy
Frequency
q y υ / GHz Hres / G
band for ge
S 4.0 ~1400
(a.k.a. ESR, EMR)
X 9.0 ~3200
(most common)
Electromagnets
Lecture II. Isotropic (fluid
Q 34 ~12000
solution) spectra
W 94 ~33000 Supercon magnet

Eric McInnes & David Collison, EPSRC UK National EPR Facility & Service
Photon Science Institute, The University of Manchester
Microwave frequencies eric.mcinnes@manchester.ac.uk david.collison@manchester.ac.uk

The g-value The g-shift

•Free electron: ge = 2.002319… a fundamental constant, related to
the magnetic moment of the electron due to its spin (ang. mom.). (ii) Mixing with excited states via spin- LUMO

[Nb: gyromagnetic ratio γe = geβe/ħ; magn. mom., µe = -geβe√S(S+1) orbit coupling (SOC) → small orbital
moment ∝ 1/∆E. SOMO
•In real materials, measured g ≠ ge. g ~ ge for orbital singlets (A or B terms).
terms)
Normal range 3 > g > 1. HOMO
g ∝ 1/Hres ⇒ higher g at lower field. Often discussed as
• …because of orbital angular momentum a 2 nλ the g-shift:
contribution to the magnetic moment. g = ge −
∆E ∆g = g - ge
• Can be:

(i) Ground state (T or E terms) → large

orbital moment; need to treat spin-orbit
split states. Complicated, and won’t
consider further here.
λ = SOC constant - larger for heavier elements.
a2 (≤ 1) = covalency parameter
e.g. Oh Co2+; 4T n = quantum mechanical coefficient

2
 Trends in g-shift a 2nλ Hyperfine Coupling mS = +1/2
mI = +1/2
g = ge −
∆E •If electron spin interacts with e.g. S = ½ with I = ½ A/2
Consequently: nuclear spin (I) mS = +1/2
(i) Organic free-radicals: usually large ∆E (colourless), small λ. → hyperfine structure, with mI = -1/2
hydrocarbon radicals → g ≈ 2.002-2.003 coupling constant A (or a).
N/O-based radicals g ≈ 2.003-2.006
S-based radicals g ≈ 2.007-2.010 •Analogous to nuclear spin- mS = -1/2
mI = -1/2
(ii) transition metal ions: small ∆E (coloured; crystal field nuclear spin (J) coupling in
A/2
splittings), big λ → g significantly different from ge. NMR.
mS = -1/2
mI = +1/2
( ) g can be < or > ge.
(iii) •2nd selection rule: ∆mI = 0
AA
Coupling with filled orbital → +ve contribution to ∆g.
Coupling with empty orbital → -ve contribution to ∆g. •Each transition corresponds
to a given value of mI
e.g. {VIVO}2+, d1 typical g ≈ 1.9 →2I+1 transitions. g
e.g. Cu2+, d9 typical g ≈ 2.1 mI = +½ mI = -½
Magnetic Field

Coupling Patterns Triangles for I > 1/2 nuclei

•Coupling to n equivalent spin I nuclei → 2nI+1 multiplet. n × (I = 1); add up 2I + 1 = 3 numbers
•Relative intensities from triangles or stick spectra (as for NMR).

•E g for coupling to n equivalent I = ½ nuclei

•E.g. nuclei…Pascal’s
Pascal’s triangle
“add up 2I + 1
numbers to
obtain the next row” n × (I = 3/2 ); add up 2I + 1 = 4 numbers
n 0 1 0 # Σ
1 0 1 1 0 2 2
2 0 1 2 1 0 3 4
3 1 3 3 1 4 8
4 1 4 6 4 1 5 16 n × (I = 5/2 ); add up 2I + 1 = 6 numbers
5 1 5 10 10 5 1 6 32
6 1 6 15 20 15 6 1 7 64
7 1 7 21 35 35 21 7 1 8 128
8 1 8 28 56 70 56 28 8 1 9 256
Can observe coupling to quadrupolar nuclei, even if in low symmetry

3
 Methyl radical 2,2-diphenyl-1-picrylhydrazyl
H
H
C H (dpph)
doublet of
1:3:3:1 quartets

× 20
O2N
aH
N N NO2

O2N
aC
•14N, 100% nat. ab., I = 1
1:3:3:1 quartet
•Two very similar couplings
•1:2:3:2:1 pentet

g = 2.00354
13C, 1.1% nat. ab., I = ½ Used as a standard for g-value calibration

[VO(acac)2]: VIV, d1 [Cu(acac)2]: CuII, d9

ν = 9.4190 GHz O O O
Cu
O V O O O
g = 1.970 O O idealised
63Cu
C 69% nat.t ab.
b
65Cu 31 % nat. ab.
AV
Both I = 3/2

g = 2.142 •Same g, different A

51V, 100% nat. ab., I = 7/2. •A(

A(63Cu)/A(
C )/A(65Cu)
C ) = ratio
ti off
•1:1:1:1:1:1:1:1 octet nuclear magnetic moments
A63Cu
•“short+fat” and “tall+thin” lines due to (gnβnI) hence nuclear gn-
3000 3200 3400 tumbling
3600 effects. 4000 → rotational
3800 Analysis values…
A65Cu
Magnetic Field /correlation
G times (hence mobility etc)
H /G
•note 2nd order effects: separations not even; g
offset from centre. 3200 3300 3400 3500 3600 = 1.484/1.588 = 0.935

4
 Other poly-isotopic examples “Superhyperfine” = ligand hyperfine
each Pt satellite has 34/
2 = 17% intensity relative to the I = 0 line 1:1:1 triplet from 14N
0.66

+
0.34

ACr
each Mo satellite has 26/
6 = 4.3% intensity relative to the I = 0 line
N
3−

0 74
0.74 NC CrV CN CrV, 3d1

+
NC CN

CN
0.26

•Unpaired electron must be partly delocalized out to 14N nucleus.

•Superhyperfine coupling is direct evidence for covalency in
coordination compounds.

Units for hyperfine coupling

•Measured in field units, but coupling constant is an interaction energy
Electron Paramagnetic •Need to convert to energy (or equivalent) units…
Resonance (EPR) Spectroscopy giso = 2.00
Aiso = 100 Gauss

(a.k.a. ESR, EMR)

From: ∆E = hν = gβeHres
βe in cm-1 G-1

A(cm-1) = g × βe × A(G)
Lecture III. Meaning of hyperfine = 2.00 × 4.66858 × 10-5 × 100
A
interaction = 93.4 × 10-4 cm-1

A(MHz) = g × A(G) / 0.7145

= 2.00 × 100 / 0.7145
Eric McInnes & David Collison, EPSRC UK National EPR Facility & Service
= 279.9 MHz
Photon Science Institute, The University of Manchester
eric.mcinnes@manchester.ac.uk david.collison@manchester.ac.uk
Conversion from field to energy units depends on the g-value

5
 Hyperfine (e-n) Mechanisms Methyl radical
H
•Dipolar (through space): Depends on e-n distance and orientation C H doublet of
w.r.t. applied field. H 1:3:3:1 quartets

Adip ∝ 3cos2θ-1 - Averages to zero in fluid solution. × 20

aH

•Spin density at the nucleus (Fermi contact): Direct contribution aC

only possible if upe is (at least partly) in an s-orbital (p,d,f
(p d f orbitals 1:3:3:1 quartet
have nodes at the nucleus).
•Spin-orbit coupling [∝ ∆g]: important for d-block
Often see solution hyperfine where
⇒Should only see s-electron density in solution, but… symmetry should preclude it!

Spin Polarisation McConnell analysis

•Unpaired electron interacts differently with the ↑ and ↓ electrons in Calculation of spin population of 2pz orbital in π-radical from
a filled orbital hyperfine coupling to bound H
•→the paired electrons have slightly different spatial distributions.
π(pz) π(pz) CH3• radical H
C H
H

C H C H H
aiso = ρQ
σ(C-H) σ(C-H) C6H6-• radical
H H
C C
Spin density in H C C H
C 2pz orbital C C
H H
•Slightly favoured by spin correlation (cf. Hund’s rule) ρ = 1, Q = 23 G
•“excess” spin up at C; spin down at H – including nucleus.
1:6:15:20:15:6:1 septet
3.75 G
3.75 1
•Or, configuration interaction between pz1σ2 with excited states ρ= ≈
23 6
•Similar arguments for observation of 13C splitting or, e.g., metal
hyperfine in d-block complexes

6
Structural information from hyperfine
•Radical identification
•Geometric structure can be inferred, e.g… Electron Paramagnetic
α2 =
38
= 0.028 CH3• radical Resonance (EPR) Spectroscopy
1347
AC = 38 G H
C H
H (a.k.a. ESR, EMR)
Hyperfine for unit
population of
13C 2s orbital = 1347 G

(from theory)
Lecture IV. What happens when we
F
C immobilise the sample?
F
AC = 272 G F
272
α2 = ≈ 0.2 CF3• radical Eric McInnes & David Collison, EPSRC UK National EPR Facility & Service
1347
Photon Science Institute, The University of Manchester
eric.mcinnes@manchester.ac.uk david.collison@manchester.ac.uk

Sample phase and orientation g anisotropy

•Remember g ≠ ge due to excited state orb. ang. mom. via SOC.
•in fluid solution molecules tumbling rapidly (mostly) on timescale •Different excited states contribute to magnetic moment (hence g) in
of experiment. different orientations. Easiest to see by example.
•Magnetic field “sees” average orientation of the molecule.
→ “isotropic” spectrum.
spectrum •Consider a square planar Cu(II) complex
complex, D4h symmetry.
symmetry
•…but molecules are not, in general, isotropic. They look different
x2-y2 (b1g)
from different orientations.
•As with ALL spectroscopies, spectrum depends on the orientation of z2 (a1g)
the molecule (e.g. polarisation of optical transitions). EPR easy to
xy (b2g)
measure on powders, single crystals, frozen solutions etc.
xz, yz (eg)

L L
z
•e.g. sq. planar CuII (D4h) Oh (2E) D4h (2B1g)
2A 2B 2E
1g 2g g
•g and A will depend on
N L
L
Cu
Lz
L S orientation of molecule (can
L L define by C4) w.r.t. H. Upe in x2-y2 Excited states

7
 Hand-wavey approach …or from group theory
•Non-zero orbital ang. mom. if orbitals can be transformed by D4h E 2C4 (z) C2 2C'2 2C''2 i 2S4 σh 2σv 2σd
rotation about an axis. E.g… A1g +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 - x2+y2, z2
A2g +1 +1 +1 -1 -1 +1 +1 +1 -1 -1 Rz -

(i) x2-y2 transforms to xy via Rz B1g +1 -1 +1 +1 -1 +1 -1 +1 +1 -1 - x2-y2

B2g +1 -11 +1 -11 +1 +1 -11 +1 -11 +1 - xy
x x Eg +2 0 -2 0 0 +2 0 -2 0 0 (Rx, Ry) (xz, yz)
A1u +1 +1 +1 +1 +1 -1 -1 -1 -1 -1 - -
Rz
A2u +1 +1 +1 -1 -1 -1 -1 -1 +1 +1 z -
B1u +1 -1 +1 +1 -1 -1 +1 -1 -1 +1 - -
y y
B2u +1 -1 +1 -1 +1 -1 +1 -1 +1 -1 - -
Eu +2 0 -2 0 0 -2 0 +2 0 0 (x, y) -

•∴contribution to magn.
magn moment along z from xy excited state •Orb
Orb. ang.
ang mom.
mom along z,z x or y axes has rotational vector
• and contribution to g measured with H parallel to z - “gz” symmetry rep., Ri (think about “orbiting about that axis”).
•Multiply symmetry rep. of ground state by Ri.
a 2 nλ B1g (x2-y2) . A2g (Rz) = B2g
g z = ge −
E x 2 − y 2 − E xy
∴ SOC along z mixes B1g ground state with B2g excited state (xy)

…or from group theory Result…

•D4h symmetry Cu(II) complex.
D4h E 2C4 (z) C2 2C'2 2C''2 i 2S4 σh 2σv 2σd
A1g +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 - x2+y2, z2
x2-y2 (b1g)

a 2 nλ
A2g +1 +1 +1 -1 -1 +1 +1 +1 -1 -1 Rz -
B1g +1 -1 +1 +1 -1 +1 -1 +1 +1 -1 - x2-y2
z2 (a1g) z x,y g z = ge −
B2g +1 -1
1 +1 -1
1 +1 +1 -1
1 +1 -11 +1 - xy E x 2 − y 2 − E xy
Eg +2 0 -2 0 0 +2 0 -2 0 0 (Rx, Ry) (xz, yz) xy (b2g)
A1u +1 +1 +1 +1 +1 -1 -1 -1 -1 -1 - -
xz, yz (eg)
A2u +1 +1 +1 -1 -1 -1 -1 -1 +1 +1 z - a 2 nλ
g x = g y = ge −
B1u +1 -1 +1 +1 -1 -1 +1 -1 -1 +1 - -
Oh (2E) D4h (2B1g) E x 2 − y 2 − E xz , yz
B2u +1 -1 +1 -1 +1 -1 +1 -1 +1 -1 - -
Eu +2 0 -2 0 0 -2 0 +2 0 0 (x, y) -
•g-values are anisotropic
•SOC
SOC along
l x(y)…
( ) •Can predict that gz > gx = gy (> ge)
•Exercise: z2 ground state for d9 (e.g. Jahn-Teller compressed CuII).
B1g (x2-y2) . Eg (Rx,y) = Eg •Should find gx = gy > gz (= ge)
∴ SOC along x(y) mixes B1g ground state with Eg (xz,yz) Pattern of g-values tells you about the orbital in which
the unpaired electron is located.

8
 The magic pentagon How does this affect spectra?
•Contributions to g-values summarised in…
•Fluid solution: field “sees” AVERAGE orientation

z2 g gg-value,, labelled giso

•Measure average
gy gx
6 6
gz a 2 nλ gx + g y + gz
xz yz g = ge −
2
gx gx ∆E giso =
gy 2
2 2
2 gy 3
x2-y2 8 xy
gz

•Start at a vertex for a given ground state

•Links give contributions to gi-values
•Coefficients n also given

Single orientation spectra Powder spectra and “road maps”

(e.g. single crystal) gz gx = gy z
•Each spectrum looks “isotropic”
L L
•e.g. measure xz plane for our D4h CuII example; gz > gx z Cu
L L
z
L L
Cu powder
L L
y
x
x

•Molecule has axial (disc-like)

symmetry
t (D4h)
z •Unique z
H •Whole plane of xy

•Powder spectrum is the SUM over ALL orientations

•Features observed at turning points in road map
•If we sum these, the “in-between” orientations cancel out •Different shapes and intensities due to summation

9
 Powder spectra and symmetry
z = “parallel” Electron Paramagnetic
x,y = “perpendicular”
Resonance (EPR) Spectroscopy
gz > gx = gy
(a.k.a. ESR, EMR)
gz < gx = gy
isotropic Lecture V. Information about
gx = gy = gz
e.g. Oh, Td rhombic electronic structure
axial gx ≠ gy ≠ gz
e.g. D4h, C4v, D3h, etc e.g. C2v, D2h, C2h, etc
Eric McInnes & David Collison, EPSRC UK National EPR Facility & Service
Photon Science Institute, The University of Manchester
eric.mcinnes@manchester.ac.uk david.collison@manchester.ac.uk
Arrows denote positions used to measure g-values

Information from g-values Powder spectra with hyperfine: I = 1/2

Ax = Ay
Ni3+, 3d7
isotropic

Az
N axial

• pattern of g-values can identify SOMO

• dxy or dx2-y2 : gz > gx,y > ge
• dz2 : gx,y > gz = ge
Krüger and Holm, Inorg. Chem., 1987, 26, 3645.
rhombic
•Each g-feature is split by hyperfine.
•Hyperfine coupling is also anisotropic, determined by symmetry.

10
 Powder spectra: A vs. g-anisotropy More on hyperfine
•If A > separation between g in field units, then “parallel” and
“perp” regions will overlap. Very common. •Fluid solution: field “sees” AVERAGE orientation
•E.g. typical {VO}2+: gz = 1.93, gx,y= 1.98, Az = 170 G, Ax,y = 60 G •Measure average A-value, labelled Aiso
gx,y 500 G
gx,y
Ax + Ay + Az In energy (cm-1) or
Aiso = frequency units (MHz)
3 – NOT field units.

•Aiso, Ax, Ay and Az can be either sign. No direct information in

gz
gz spectrum, BUT…
9.4 GHz 94 GHz •Can get relative signs from averaging to Aiso.
H0(gx,y)-H0(gz) = 88 G H0(gx,y)-H0(gz) = 880 G
•Can also use Aiso to determine unresolved anisotropic component.

Hyperfine Anisotropy Dipolar part of hyperfine

Adip ∝ µez µnz

(3cos θ − 1)
2

r3
H z
Remember:
•Spin density at nucleus: As θ = 0o 3cos2θ = +2
•SOC [= P∆giso] Aiso θ = 90o 3cos2θ = -1

•Dipolar, Adip: Depends on e-n distance and orientation w.r.t. applied

θ e
field.
field
r
•In solid state, observe SUM of the isotropic and dipolar part. n
A = Aiso + Adip
Any dipolar interaction has form
+2a, -a, -a

11
 Electron in a pz-orbital Determining spin density distribution
Angular factor from Hyperfine observed for
fluid soln
form of wavefunction unit population of a p- Methf, 213 K

4 2 orbital for that isotope.

Az = Aiso + a Pp Calcd from theory.1 Aiso(P) = ±28 G → ±26x10-4 cm-1
Exptly 5
observed 2
hyperfines Ax ( y ) = Aiso − a 2 Pp
5
Covalency, a2 ≤ 1. frozen
Az(P) = ±118 G → ±110x10-4 cm-1
Ax,y(P) = 15 G → 14x10-4 cm-1
± ±
a = MO coefficient 123 K
6 2
Az − Ax ( y ) = a Pp of pz in SOMO.
5

Anisotropic hyperfine → composition of molecular orbitals!
1. J.R. Morton and K.F. Preston, J. Mag. Reson. 1978, 30, 577;
P.H. Rieger, J. Magn. Reson. 1997, 124, 140.
•Aiso = (Ax +Ay +Az)/3 ⇒ Ax,y and Az must be opposite sign.
•Assume Az –ve → -ve a2. Not physically meaningful.
•Az +ve → a2 = 0.45, i.e. 45% of spin density in P 3pz.
Pp = +306x10-4 cm-1 for 31P (100% nat. ab., I = ½)

Electron in a dxy/x2-y2 orbital Example: covalency in CuII complexes

Hyperfine for unit Different angular
population of a d- factor for d-orbitals SOC (excited state) gz
orbital. contribution.
Convenient to cast in
⎡ 4 2 5 ⎤
Az = Aiso + Pd ⎢− a 2 + ∆g z − ∆g x, y ⎥
terms of g-shifts,
g-shifts O O
Cu
⎣ 7 3 21 ⎦ because these can be O O
⎡ 2 1
Ax, y = Aiso + Pd ⎢ + a 2 − ∆g z +
5 ⎤
∆g x, y ⎥
measured. gx,y region
⎣ 7 3 42 ⎦
Solve for a2: spin density in d gz
⎡ 6 5 ⎤
Az − Ax, y = Pd ⎢ − a 2 + ∆g z − ∆g x, y ⎥ S S
⎣ 7 14 ⎦ Et2N Cu NEt2
S S

Electron in a dz2 orbital

⎡ 4 1 17 ⎤
Az = Aiso + Pd ⎢+ a 2 − ∆g z − ∆g x, y ⎥ gx,y
⎣ 7 3 21 ⎦ 9.5 GHz
CH2Cl2/tol, 100 K
⎡ 2 2 1 17 ⎤ H/G
Ax, y = Aiso + Pd ⎢− a − ∆g z + ∆g x, y ⎥
⎣ 7 3 42 ⎦ 2600 2800 3000 3200 3400 3600 3800

12
 Example: covalency in CuII complexes Example: covalency in CuII complexes
x,y
z
O O Aiso = 76x10-4 cm-1
O O Cu gz = 2.260, gx,y = 2.050
Cu O O
Az = 189x10
189 10-44 cm-11, Ax,y = 20x10
20 10-44 cm-11
O O
Higher frequency
(field) pulls g-values S S Aiso = 75x10-4 cm-1
apart on field scale z Et2N Cu NEt2 gz = 2.085, gx,y = 2.035
S S
S S Az = 175x10-4 cm-1, Ax,y = 38x10-4 cm-1
Et2N Cu NEt2
S S

x,y •Aiso, Az and Ax,y all same sign (-ve)

⎡ 6 5 ⎤
•CFT predicts x2-y2 ground state Az − Ax, y = Pd ⎢ − a 2 + ∆g z − ∆g x, y ⎥
35 GHz ⎣ 7 14 ⎦
CH2Cl2/tol, 100 K
•→a2 = 0.77 for O-donor complex
H/G
•→a2 = 0.48 for S-donor complex
11000 11500 12000 12500 •Spin much more delocalised (i.e. greater covalency) for S-donor

13