UNIT-IV

NQR and EPR spectroscopy

Electron paramagnetic resonance spectroscopy: theory of EPR spectroscopy,

presentation of the spectrum, nuclear hyperfine splitting in isotropic systems. EPR

spectra of anisotropic systems: anisotropy in g-value causes of an isotropy,

anisotropy in hyperfine coupling. Double resonance in ESR, Zero field splitting and

Kramer’s degeneracy.

Theory and Principle of NQR spectroscopy-Nature of electric field gradient, Energy

levels and selection rules, Interaction of electric quadrupole with electromagnetic

radiation, nuclear orientations, the asymmetry parameter, quadrupole transitions in

spherical, axially symmetric fields and not axially symmetric fields. Applications of

NQR spectra

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Theory of EPR spectroscopy

 Electron paramagnetic resonance (EPR) or electron spin resonance (ESR)

spectroscopy is a method for studying materials with unpaired electrons.

 ESR is observed in microwave region while NMR is observed in radio

frequency region of the electromagnetic spectrum.

 The basic concepts of EPR are analogous to the nuclear magnetic resonance

(NMR), but it is electron spins that are excited instead of the spins of atomic

nuclei.

 EPR spectroscopy is particularly useful for studying metal complexes or

organic radicals.

 One of the most important uses of ESR technique lies in the detection of

extremely short-lived (transient) free radical intermediate in chemical

reactions.

Electron Zeeman Interaction

For an isolated electron, without any outside forces, it has only an intrinsic

angular momentum called “spin.” Because an electron is charged, the

angular/spinning motion of this charged particle generates a magnetic field. In other

words, the electron due to its charge and angular momentum, acts like a little bar

magnet, or magnetic dipole, with a magnetic moment ().

The electron with spin 1/2, the parallel state () is designated as ms = –1/2 and

the antiparallel () state is ms = +1/2 (Fig. 1A). The energy of each orientation is the

product of  and B0.

E =  B0 where,  = ms g β

β is a conversion constant called the Bohr magneton (also called B) and ge is

the spectroscopic g-factor of the free electron and equals 2.0023192778 (2.00).

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Therefore, the energies for an electron with ms = +1/2 and ms = –1/2 is, respectively,

as follows

E = ms g β B0

E1/2 = +1/2 g β B0 E–1/2 = –1/2 g β B0

Spine-Orbit Interaction

Consider an electron placed in an atom or molecule (Fig. 1B). The spin angular

momentum and orbital angular momentum is produces the magnetic moment.

These two magnetic moments couple with each other called spin-orbit interaction

and the energy of this interaction depends on their orientations.

(Figure 1: (A) Electron Zeeman interaction and (B) Spin-orbit coupling)

The magnitude of the spin-orbit coupling contribution depends on the size of

the nucleus containing the unpaired electron. Therefore, organic free radicals, with

only H, O, C, and N atoms will have a small contribution from spin-orbit coupling,

producing g-factors very close to ge. In the above system, spin-orbit coupling are

negligible. While the g-factors of much larger elements, such as metals and their

complexes, may be significantly different from ge. Hence, the term EPR is used for

these unpaired systems with significant spin-orbit coupling.

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Presentation of ESR Spectra

In an EPR spectrometer, a paramagnetic sample is placed in a uniform

magnetic field B0 which, splits the energy levels of the ground state by

ΔE = hυ = gβB0 ----------- (1)

The value of g can be determined from the ΔE, the energy difference between

the two spin levels. This can be done by both irradiating the sample either with MWs

with a fixed frequency and sweeping the magnetic field or applying a constant

magnetic field and scan the frequency of the electromagnetic radiation as in

conventional spectroscopy (Fig. 2).

The direct detection of the absorption signal is possible only for samples

containing a high concentration of unpaired electrons. The phase sensitive detector

technique was used to reduce the noise and gives the first derivative of signal as

shown in Fig. 2.

Furthermore, due to short relaxation time of paramagnetic compounds, the

absorption signals are usually broad and hyperfine splitting are buried and not seen

(Fig. 2B). However, the derivative signal observed using field modulation exhibits

well resolved hyperfine features.

(Figure 2: Absorption and first derivative electron paramagnetic resonance spectra for single line (A)

and multiple lines (B) systems)

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Spectral parameters

1. An unpaired electron can gain or lose angular momentum, which can change

the value of its g-factor, causing it to differ from ge. This is important for

chemical systems with transition-metal ions

2. The magnetic moment of a nucleus with a non-zero nuclear spin will affect

any unpaired electrons associated with that atom. This leads to the

phenomenon of hyperfine coupling, analogous to J-coupling in NMR,

splitting the EPR resonance signal into doublets, triplets and so forth.

3. Interactions of an unpaired electron with its environment affect the shape of

EPR spectral line. Line shapes can give the information about, for example,

rates of chemical reactions.

4. The g-factor and hyperfine coupling in an atom or molecule may not be the

same for all orientations of an unpaired electron in an external magnetic field.

This anisotropy depends upon the electronic structure of the atom or

molecule (e.g., free radical) and it can provide information about the atomic

or molecular orbital containing the unpaired electron.

ESR Reference Samples

1. DPPH has been widely used g-value marker. It has also been used as a

standard also for signal intensity. DPPH is stable in the solid state but

solution state it is strongly depending upon the solvent (more stable in

acetonitrile solution).

2. For transition metal samples, S = 1/2 Cu(II) and S = 5/2 Mn(II) are commonly

used. CuSO4.5H2O, Cu(II)EDTA, and MnSO4.H2O (available with 99% purity)

are used as standard.

3. VOSO4.nH2O also has variable number of waters of hydration. So, it was

titrated with KMnO4 in the usual volumetric analysis method to determine

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 the V(IV) content and used as standard. The compound was used as the solid,

and in some cases ground with NaCl or KCl.

4. The g-values of some common EPR standards are as follows: DPPH (2.0037 ±

0.0002), Perylene cation in 98% H2SO4 (2.00258 ± 0.00002), p-

Benzosemiquinone in butanol-KOH at 290 K (2.004679 ± 0.0000129), Fremy’s

salt K2NO(SO3)2 (2.0057), tetra-cyano-quinoidimethane-lithium salt C12H4N4Li

(g = 2.00252), CuSO4.5H2O (g(Parallel) = 2.27 and g(Perpendiculer) = 2.08), Cu(acac)2 in

toluene solution (g = 2.13 and 2.126), VOSO4.5H2O (1.99), VO(acac)2.(2.00),

VOTPP (tetraphenyl porphyrin) (1.958).

Solvents in EPR

 Solvents should NOT absorb the Microwave (MW) radiation.

 Solvents with high dielectric constant (e.g., water and alcohol) cannot be used,

because it absorbs the MW radiation.

 EPR – obtained for gas, solution, powder, single crystal, frozen solution.

 Toluene, Glycerol, Isooctane, Conc. H2SO4, methanol+ethanol mixture,

Toluene+chloroform mixture

Hyperfine splitting

This splitting occurs due to hyperfine coupling (the EPR analogy to NMR’s J

coupling) and further splits the fine structure (occurring from spin-orbit interaction)

of the spectra of atoms with unpaired electrons.

Hyperfine Splitting is used in EPR spectroscopy to provide information about a

molecule, most often radicals. The number and identity of nuclei can be determined,

as well as the distance of a nucleus from the unpaired electron in the molecule.

Hyperfine coupling is caused by the interaction between the magnetic

moments arising from the spins of both the nucleus and electrons in atoms. As

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shown in figure, in a single electron system, the electron with its own magnetic

moment moves within the magnetic dipole field of the nucleus.

(B is magnetic field, μ is dipole moment, ‘N’ refers to the nucleus, ‘e’ refers to the electron)

This spin interaction in turn causes splitting of the fine structure of spectral

lines into smaller components called hyperfine structure. Hyperfine structure is

approximately 1000 times smaller than fine structure. The figure shows, the

comparison of fine structure with hyperfine splitting structure for hydrogen.

The total angular momentum of the atom is represented by F with regards to

hyperfine structure. This is found simply through the relation F = J+I, where I is the

ground state quantum number and J refers to the energy levels of the system.

The coupling patterns due to hyperfine splitting are the same to that of NMR.

The number of peaks resulting from hyperfine splitting of radicals may be predicted

by the following equations where Mi is the number of equivalent nuclei,

# of peaks = MiI + 1 for atoms having one equivalent nuclei

# of peaks = (2M1I1 + 1) (2M2I2 + 1) ...., for atoms with multiple equivalent nuclei

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 For example, in the case of a methyl radical, 4 lines would be observed in the

EPR spectra. A methyl radical has 3 equivalent protons interacting with the unpaired

electron, each with I = 1/2 as their nuclear state yielding 4 peaks.

(Approximate peaks resulting from hyperfine splitting between two unequivalent protons)

When I = 1/2 as in the case for 1H, 19F and 31P, the intensity of the lines produced

follow Pascal's triangle. Using the methyl radical example, the 4 peaks would have

relative intensities of 1:3:3:1. The following figures show the different splitting that

results from interaction between equivalents versus non-equivalent protons

(Approximate peaks resulting from hyperfine splitting between two equivalent protons)

It is important to note that the spacing between peaks is 'a', the hyperfine

coupling constant. This constant is equivalent for both protons in the equivalent

system but unequal for the unequivalent protons.

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Isotropic and Anisotropic Interactions

Electron-nuclei interactions have several mechanisms; the most common is

Fermi contact interaction and dipole interaction. Dipole interactions occur between

the magnetic moments of the nucleus and the electron (electron moves around a

nucleus).

However, as an electron approaches a nucleus (it has also magnetic moment).

When this magnetic moment moves very close to the nucleus, results electron and

nucleus are in contact radically and the removal of dipolar interaction. The

interaction of these magnetic moments occurs when the electron is outside the

nucleus. This non-dipolar interaction of a nucleus and electron spin in contact is

called Fermi contact interaction. A comparison of this is shown in the figure. The

sum of these interactions is the overall hyperfine coupling of the system.

(Different electron-nuclei interactions resulting in hyperfine coupling)

Fermi contact interactions predominate with isotropic interactions, meaning

sample orientation to the magnetic field does not affect the interaction. Due to the

fact that, this interaction only occurs when the electron is inside the nucleus, only

electrons in the s orbital exhibit this kind of interaction. All other orbitals (p,d,f)

contain a node at the nucleus and can never have an electron at that node. The

hyperfine coupling constant in isotropic interactions is denoted 'a'.

Dipole interactions predominate with anisotropic interactions, meaning sample

orientation does change the interaction. These interactions depend on the distance
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between the electron and nuclei as well as the orbital shape. The typical scheme is

shown in the figure.

(Interaction between two diploes with radius 'r')

Dipole interactions can allow for positioning paramagnetic species in solid

lattices. The hyperfine coupling constant in isotropic interactions is denoted 'B'.

Nuclear hyperfine splitting in isotropic systems

Hyperfine structure (HFS) occurs as a result of the magnetic interaction

between the electronic spin S and the nuclear spin I. The magnitude of this

interaction is given by A called isotropic hyperfine coupling constant. The hyperfine

interaction in ESR spectra is analogous to the fine structure, i.e., nuclear spin-spin

interaction in NMR spectra. As a result of this interaction, the ESR signals or peaks

are further split into several lines (HFS).

Characteristics of isotropic hyperfine splitting

1. It depends on the magnitude of magnetic moments of nuclear and electron

spins.

2. The electron spin density in the immediate vicinity of the nucleus (Fermi

contact)

3. It is independent of applied magnetic field

4. It obeys (n + 1) rule for I = 1/2 i.e., (2nI + 1)

5. The intensity ratio is obtained using Pascal triangle (analogous to NMR spin-

spin coupling)

6. Let us consider the hyperfine interaction in the following examples to

illustrate and characterize the radicals: (1) hydrogen atom; (2) methyl radical;

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 (3) (2,2,6,6-tetramethylpiperidin-1-yl)oxyl; (4) 1,4-benzosemiquinone radical

anion; (5) naphthalene negative ion radical; (6) p-Nitrobenzoate dianion

radical, etc.

1. EPR of Hydrogen Atom

It contains an unpaired electron with S = 1/2 and a proton with nuclear spin I =

1/2 (ms = ± 1/2 and mI = ± 1/2). In the absence of magnetic field (B0 = 0), the electron

spin energy levels are degenerate, i.e., have the same energy (Fig. 3). By applying the

magnetic field, produce the degeneracy between them (the ms = – 1/2 sublevel going

down and the ms = + 1/2 sublevel going up). Each of these electron sublevels further

interacts with the nucleus (I = 1/2) giving four sublevels designated by the value of

mI. This phenomenon is called hyperfine splitting.

The selection rule for hyperfine transitions is given below,

Δms = ± 1; ΔmI = 0

On using the selection rule, equally intense two ESR lines are obtained, i.e., a

doublet is observed, as shown in Fig. 3.

(Figure 3: The energy level diagram (A) and hyperfine structure (B) in the electron spin resonance

spectrum of hydrogen atom)

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2. Methyl Radical

It contains an unpaired electron with S = 1/2 and three equivalent protons. Each

proton has a spin I = 1/2. Therefore, the total nuclear spin is I = 3/2. For each ms = ±

1/2, the mI values are +3/2, +1/2, –1/2, –3/2 as shown in Fig. 4. The interpretation of

the ESR spectrum is similar to that of H atom. The ESR spectrum shows four equally

spaced lines, (n + 1), i.e., a quartet in the intensity ratio 1:3:3:1. The spacing between

any two successive lines represents the isotropic coupling constant (A).

In methyl radical,

1 Proton-splits into 2 lines 1:1

2 Proton-splits into 3 lines 1:2:1

3 Proton-splits into 4 lines 1:3:3:1

(Figure 4: ESR spectrum of methyl radical)

3. (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (Nitroxide)

(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl is a nitroxide abbreviated as TEMPO. It

is a stable free radical with an unpaired electron delocalized between oxygen and

nitrogen atoms. As, nitrogen has I = 1, each Ms = ±1/2 splits into three levels MI = –1,

0, +1 giving rise to three peaks of equal intensity as shown in Fig. 5.

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 (Figure 5: ESR spectrum of (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl)

4. p-Benzosemiquinone Radical Anion

This anion radical has one unpaired electron (S = 1/2) interacting with four

equivalent protons. The number of peaks observed is calculated as (2nI + 1 = 2 × 4 ×

1/2 + 1 = 5). For four equivalent protons (I = 2), MI values are +2, 1, 0, –1, –2.

Therefore, the ESR spectrum (Fig. 6) contains a quintet, i.e., five equally spaced lines

with the intensity ratio 1:4:6:4:6:1.

(Figure 6: ESR spectrum of p-benzosemiquinone radical anion)

5. Cyclopentadienyl Radical

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 This radical has one unpaired electron (S = 1/2) interacting with five equivalent

protons. Hence, the number of peaks observed is calculated as (2nI + 1 = 2 × 5 × 1/2 +

1 = 6). Therefore, the ESR spectrum (Fig. 7) contains a sextet i.e., six equally spaced

lines.

(Figure 7: ESR spectrum of the cyclopentadienyl radical)

6. Benzene Anion Radical

This radical has one unpaired electron (S = 1/2) interacting with six equivalent

protons. Hence, the number of peaks observed is calculated as (2nI + 1 = 2 × 6 × 1/2 +

1 = 7). Therefore, the ESR spectrum (Fig. 8) contains a septet, i.e., seven equally

spaced lines.

(Figure 8: ESR spectrum of the benzene anion radical)

7. Naphthalene Anion Radical

This radical anion consists of one unpaired electron interacting with two sets (α

and β) of four equivalent protons each as shown in Fig. 9. The ESR spectrum would

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thus show, i.e., (2nI1 + 1) × (2nI2 + 1) = (4 + 1) × (4 + 1) = 25 lines. This radical is formed

when naphthalene in solution in 1,2-dimethoxyethane is reduced with potassium

metal. A green colored solution is obtained whose EPR spectrum is shown below. By

considering the pattern and coupling constants of a1 = 4.90 G and a2 =1.83 G of

hyperfine splittings, the species formed is consistent with the naphthalene radical

anion.

(Figure 9: ESR spectrum of naphthalene anion radical (K+ is the counter ion) at 298 K)

8. p-Nitrobenzoate Dianion Radical

The structure, experimental spectrum and its stick diagram for the

reconstruction of the spectrum for the p-nitrobenzoate dianion radical are shown in

Fig. 10. The unpaired electron in the molecule first interacts with the 14N (I = 1) with

large splitting (AN) to give a triplet signal of intensity ratio 1:1:1. Furthermore, it

consists of two sets of two equivalent protons. So, each split again into a triplet with

intensity ratio 1:2:1 and again each signal splits into triplet to give overall 27 lines as

shown in Fig. 10. However, there is no way based on the spectrum alone to decide

which splitting corresponds to which set of protons. A comparison was made with

the calculated results and with spectra of similar radicals for which deuterium

substituted radicals have been studied. It indicates that the smallest splitting, A H’, is

associated with the protons closer to the CO2, while the relatively large splitting, AH,

corresponds to the protons near to the NO2 group.

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 (Figure 10: ESR spectrum of p-Nitrobenzoate dianion radical)

9. Diphenylpicrylhydrazyl Radical

In the case of DPPH, the unpaired electron is delocalized on to two nitrogen

nuclei (I = 1 and n = 2). Hence, the two nitrogen nuclei are equivalent and the

spectrum (Fig. 11) exhibits 2nI + 1 = 5, five lines with intensity ratio: 1:2:3:2:1.

However, in its solid polycrystalline form, it exhibits a single-EPR line that is

narrowed due to Heisenberg spin exchange.

(Figure 11: ESR spectrum of diphenylpicrylhydrazyl radical)

Factors affecting the Magnitude of g-values

The g-value is given by the expression for an unpaired electron in a gaseous

atom or ion, for which Russell-Saunders coupling is applicable as follows,

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 𝐽 𝐽 + 1 + 𝑆 𝑆 + 1 − 𝐿(𝐿 + 1)
𝑔 =1+
2𝐽(𝐽 + 1)

S (total spin angular momentum quantum no.) = s1 + s2 + s3....., L (total orbital

angular momentum quantum no.) = l1 + l2 + l3...., and J (total angular momentum

quantum no.) =|L + S|.

1. For a free electron (S = 1/2, L = 0, J = 1/2), the g-value, 2.0 is determined from

the above equation. However, the actual value for a free electron is 2.0023

where the contribution 0.0023 is due to a relativistic correction.

2. In the case of gaseous halogen atoms, the g-values predicted by the equation

were found to agree exactly with the observed values. All the halogen atoms

posses the same ground state term (2P3/2, L = 1, S = 1/2, J = 3/2). On substituting

these values in the equation, it yields g = 4/3, identical with the experimental

value.

3. When the unpaired electron is placed in a chemical/crystal field environment,

either in a free radical, or especially in a transition metal ion complex, there is

no such agreement observed. This equation is not applicable.

4. For most free radicals, spin-orbit coupling is very small and negligible. So, the

g-values are nearly equal to the free-electron value. The small deviations

(±0.05 or smaller) often observed are accounted for by a mixing of low-lying

excited states with the ground state. Therefore, the g-values are of limited use

for free radicals.

g-Tensor and Anisotropy

The spin Hamiltonian term describing the interaction between an electron spin

and the external applied magnetic field (B) is given by

ĤEZ = BBTgŜ

In the electron Zeeman interaction, the g-value depends on the absolute

orientation of the molecule with respect to the external magnetic field. The
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orientation of the molecule can be characterized by the elevation angle θ between

the molecular z-axis and the vector of the magnetic field B. ϕ denotes the angle

between its projection on the molecular xy-plane and the x-axis as shown in

(Orientation of the magnetic field B with respect to the coordinates (x,y,z) of the molecule)

For anisotropic spectrum, the effective g-value depends on both spherical

angles and hence the angular dependency of the g-value can be calculated by

2 2 2 1
𝑔 𝜃, 𝜑 = (𝑔𝑋𝑋 𝑆𝑖𝑛2 𝜃 𝐶𝑜𝑠 2 𝜑 + 𝑔𝑌𝑌 𝑆𝑖𝑛2 𝜃 𝑆𝑖𝑛2 𝜑 + 𝑔𝑍𝑍 𝐶𝑜𝑠 2 𝜃) 2

(The elevation angle θ and the azimuth ϕ in a unit sphere representing the molecular coordinate

system (collinear to the principal g-tensor, gxx, gyy, and gzz) and the magnetic field vector B0)

In the case of axial symmetry with gzz = g‖ aligned parallel to the unique axis of

the molecular frame and gxx = gyy = g⊥ aligned perpendicular to this axis, the g-tensor

is given by

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Hence, the ϕ dependence vanishes and the effective g-value is simplified as

𝑔(𝜃) = (𝑔⊥2 𝑆𝑖𝑛2 θ + 𝑔‖2 𝐶𝑜𝑠 2 𝜃)1/2

The isotropic and anisotropy broadened powder spectra for paramagnetic

species with axial and orthorhombic symmetries are displayed in the figure 1.

(Figure 1: Different pattern of electron paramagnetic resonance spectra due to g-tensor values,

Isotropic (left), axial (middle), and rhombic (right))

Depending on the magnitude of g-values, there are three classes.

1. The first class is called isotropic, where all of the principal g-factors are the

same.

2. The second class, called either axial elongated (middle top) or compressed

(middle bottom), there is a unique axis that differs from the other two (g x = gy

≠ gz) (Fig. 1). The g-factor along the unique axis is said to be parallel with it, gz

= g‖, while the remaining two axes are perpendicular to it, gx,y = g⊥.

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 3. The last class, called rhombic, occurs when all the g-factors are different, i.e.,

gx ≠ gy ≠ gz (Fig. 1, right).

Anisotropic hyperfine coupling

The hyperfine interaction can also be anisotropic and the form of the spectrum

follows directly from that of the glass spectra for an anisotropic Zeeman interaction.

For example, an s = ½ coupled to a single I = ½ could give the spectra below.

When the sample is immobilised, the dipolar interaction (as well as the Fermi

contact) give to the observed hyperfine splitting. This gives the electronic and

structural information.

Hyperfine couplings are independent of frequency/field of measurement, but

the field resolution of g-anisotropy is enhanced at higher fields. This is one

advantage of measurement at higher frequency.

The example below shows spectra for a typical nitroxide with parameters gx =

2.002, gy = 2.006, gz = 2.008, and 14N hyperfine parameters Ax = 32 G, Ay = 1 G, Az =

1 G, at different experimental frequencies. At low frequency (L-, S- and X-bands) the

spectrum is dominated by the hyperfine effects of the 14N nucleus, but at K- and Q-

band frequency the g-value anisotropy is becoming clear, and at W-band frequency

all three g-values and the three hyperfine lines from Ax are determined.

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EPR spectra of anisotropic systems

The interaction of a paramagnetic molecule with an external magnetic field is in

general described by an anisotropic g-tensor. The anisotropy reflects the coupling of

the electron spin(s) to the electrostatic field of the spatial environment.

In square planar complexes, Ni2+(d8) has no unpaired electron (square planer)

in its orbitals in Fig. 1. Therefore, it does not exhibit EPR signal at room temperature.

However, in Ni(II) octahedral or elongated complexes, there are two unpaired

electrons (S = 1), which have large ZFS and hence shows no EPR spectra (Fig. 1A).

However, under favourable conditions, it shows one EPR signal (Fig. 1A).

Example 1:

The anisotropic EPR spectrum of the Ni(II) complex in a glassy matrix at 115K

in CH2Cl2 shows g1, g2, and g3 along the three principal axes orientations in Fig. 2.

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 (Figure 1: (A) Energy level splitting of Ni(II) and (B) electron paramagnetic resonance transition)

(Figure 2: Ni(II) complex structure and its anisotropic electron paramagnetic resonance spectrum at

115K in toluene)

Example 2:

Further splittings of the main resonance line, due to hyperfine interactions, are

(to first order) independent of the microwave frequency. The compound, Tempone

(2,2,6,6- tetramethylpiperidine-N-oxyl) explain, how spectral features caused by 14N

hyperfine structure and g-anisotropy can be differentiated by measurements at X

and W-bands.

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Example 3:

EPR spectrum of semiquinone complex of monovalent copper in a frozen

toluene solution is given in the below figure. The g-anisotropy is clearly resolved at

the 2 mm band because of the better g-factor resolution. The hyperfine splitting due

to Cu and the two P atoms are not resolved at this band.

(Anisotropic ESR spectra of monovalent copper complex in frozen toluene solution, (a) 2 mm band

ESR (140 GHz). (b) 3 cm band ESR (9.6 GHz))

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Example 4:

EPR spectrum of low-spin manganese(II) complex, [Mn(dppe)2(CO)(CNBu)]2+,

(dppe = Ph2PCH2CH2PPh2), in a CH2Cl2/THF is given in the figure 1(a). The complex

has approximate C2v symmetry, while the actual symmetry is reduced to C2,

depending on the conformation of the CH2CH2 bridges of the dppe ligands.

Since it has a nominal d5 configuration, the SOMO (singly occupied molecular

orbital) is expected to be one of the t2g orbitals of an idealized octahedral complex –

dxz, dyz, or dx2-y2, is refer to C2v. The energies of the dxz and dyz orbitals are lowered by

the back-donation of π* orbitals into CO and CNBu ligands. So the SOMO is likely

based on dx2-y2.

Although the isotropic spectrum was not clearly determined, the previous

species give isotropic couplings on the order of 60–70 G; if we assume an isotropic

coupling in this range, all three matrix components must have the same sign. If the

isotropic hyperfine coupling is negative, as expected if it is arises mostly via

polarization of inner-shell s orbitals and the SOMO is mostly dx2-y2.

Example 5:

ESR spectra of [CpCo(1,3-COD)]– in frozen THF solution and [CpCo(1,5-

COD)]– in frozen DMF is given in the figure 2.

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 (ESR spectrum of [CpCo(1,3-COD)]–)

(ESR spectrum of [CpCo(1,5-COD)]–)

The 59
Co hyperfine components must have identical signs. If the signs are

negative, the isotropic couplings almost definitely arise from the polarization of

inner shell s orbitals.

Example 6:

An ESR spectrum of γ-irradiated single crystals of glycylglycine was

analyzed. The axes were defined as follows: z is along the CH bond, y is in the

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NCHC plane ⊥ to CH, and x is ⊥ to the NCHC plane. The spectral results show that,

the larger coupling to H than to N, but however there is a significant coupling to N.

ESR parameters for the glycylglycine radical

Axis g aH (G) aN (G)

x 2.0028 19 4

y 2.0035 28 3

z 2.0033 9 2

ESR parameters for the phosphonylmethyl radical

Axis g aH (G) aN (G)

x 2.0024 16.3 38.7

y 2.0029 27.2 44.3

z 2.0022 20.4 41.4

ESR parameters for the diphosphonylmethyl radical

26 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 Axis g aH (G) aN (G)

x 2.0024 12.7 36.5

y 2.0029 30.0 38.1

z 2.0022 18.5 40.4

Example 7:

The ESR spectrum of [CpCr(CO)2NO]– (Chromium Nitrosyl Complex) is

shown in below,

The g- and 14N hyperfine matrices are approximately axial for this radical, but

the g‖ axis lies close to the perpendicular plane of the hyperfine matrix. If the g ‖ axis

was exactly in the A⊥ plane, the three negative going to g‖, A⊥. In fact, the spacing

are very uneven, the second-order shifts are obtained.

Double resonance in ESR

Electron-nuclear double resonance spectroscopy (ENDOR) is an advanced

EPR technique and it is use to examine the complicated EPR spectra.

27 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

ENDOR is demonstrated by a two spin system involving one electron (S = 1/2) and

one proton (I = 1/2) interacting with an applied magnetic field.

Principle

In the steady state ENDOR experiment, an EPR transition (A, D) called the

observer and is partly saturated by microwave radiation of amplitude B1, while radio

frequency field of amplitude B2 called the pump, induces nuclear transitions. The

transitions frequencies γ1 and γ2 obey the NMR selection rules, ΔMI = ±1 and ΔMs =

0. Both the hyperfine coupling constant (a) and the nuclear Larmor frequencies are

determined using the ENDOR method.

Double electron-nuclear-double resonance (Double ENDOR) requires the

application of two RF (RF1 and RF2) fields to the sample. The change in signal

intensity of RF1 is observed while RF2 is swept through the spectrum.

Applications

1. Radical cation of 9,10-dimethylanthracene

28 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 The solution EPR spectrum of the radical cation of 9,10-dimethylanthracene

theoretically produces 175 lines due to the three sets of unequivalent protons (Fig. 1).

By comparison, the ENDOR spectrum produces only three pairs of lines (one for

each set of equivalent nuclei) from which the hyperfine couplings can be determined

directly.

2. Phenalenyl radical

The phenalenyl radical has two sets of unequivalent protons (i.e., a set of 6

and a set of 3 protons). Since the number of lines produced in an EPR spectrum is

2nI + 1, where n = number of equivalent nuclei. The first set of protons produces a

septet of lines and the second set of protons produces a quartet of lines. The EPR

spectrum is thus composed of 7 × 4 = 28 lines.

The ENDOR measurement is then performed and the resulting ENDOR

spectrum produces only four lines, with separations of 5.09 MHz and 17.67 MHz and

therefore a significantly simplified analysis.

29 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 3. [VOIV(H2O)5]2+

The ENDOR spectrum for [VOIV(H2O)5]2+ system was taken to the parallel and

perpendicular magnetic field directions.

The spectrum corresponding to θ = 0° should contain only the parallel

component of the axial proton and the perpendicular component of the equatorial

proton. Two sets of features are observed, one with a coupling of 6.3 MHz

corresponding to A‖ for the axial protons and the other with a coupling of –4.4 MHz

corresponding to A⊥ for the equatorial protons.

Assuming, a purely dipolar interaction between the protons and the electron

and the spectrum recorded at θ = 90°, resulting a coupling of 8.8 MHz corresponding

to A‖ for the equatorial protons and a coupling of –3.15 MHz corresponding to A⊥

for the axial protons and the –4.4 MHz coupling described above. It may be obtained

by the axial and equatorial protons of vanadium centre from the distances of 2.90 Å

and 2.61 Å respectively.

30 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 4. 2,3-dimethyl-1,4-benzoquinone anion radical

The reaction of 2,3-dimethylhydroquinine with sodium methoxide produces

the expected 2,3-dimethyl-1,4-benzoquinone anion radical. The EPR spectrum for

this species is based on a simple triplet of septets arising from the set of two

equivalent protons in the 5,6 positions on the aromatic ring and the six equivalent

methyl protons.

The ENDOR spectrum shows just three pairs of lines. The splitting constants

for this anion radical (with their relative signs) were therefore found to be: aH(H) = –

2.1 MHz, aH(CH3) = 8.372 MHz, aH(CH3) = 3.752 MHz and aH(OCH3) = 2.324 MHz.

31 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 5. para-O2NC6F4CNSSN

X- and Q-band EPR spectra of para-O2NC6F4CNSSN exhibited well resolved

hyperfine couplings to the two N atoms of the heterocyclic dithiadiazolyl ring and

smaller superhyperfine couplings to the two ortho19F atoms of the phenyl

substituents. The hyperfine couplings (A1, A2, A3) were determined as (39, ±2.5, ±2.5)

MHz for 14 N and (~9, ~5, ~5) MHz for 19 F, indicating that the spin distribution is

predominantly localised on the N and S atoms of the heterocyclic ring, a small spin

density is present in the perfluorophenyl ring.

The orientation selective 19F ENDOR spectra were subsequently recorded at

both X and Q-band frequencies. Analysis of these ENDOR spectra revealed the 19F

hyperfine tensors of (A1, A2, A3) = (11.4, ±3.5, ±3.5) MHz for ortho 19F and (1.0, ±0.19,

±0.4) MHz for meta 19

F suggesting spin densities of 10–3 and 10–4 magnitude

respectively for the F atoms ortho- and meta to the dithiadiazolyl ring.
32 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)
Zero field splitting and Kramers’ degeneracy

Consider the species or transition metal ions that contain more than one

unpaired electrons. In such cases, the spin degeneracy can be also resolved by the

crystal field. Thus, the spin levels may be split even in the absence of a magnetic

field due to the crystal field. This phenomenon is called zero-field splitting (ZFS) (D).

(Figure: 1. Zero-field splitting of Cr3+ ion (d3) and Co2+ (d3) high spin (S = 3/2).

33 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

(Figure: 2. Splitting of triplet state due to different magnitude of zero-field splitting,

(A) D = 0, (B) D > 0, (C) D >> 0)

There are two cases of species having either odd or even number of unpaired

electrons. For the species containing an odd number of unpaired electrons, the spin

degeneracy of every level remains doubly degenerate (Fig. 1) this is known as

Kramers’ degeneracy. However, for an even number of unpaired electrons, the spin

degeneracy of ground state may be removed completely by the crystal field (Fig. 2).

These concepts and the consequences of ZFS are used to predict how many

EPR peaks are expected for transition metal ion complexes and illustrated below

with selected examples.

Even Number of Unpaired Electrons

Consider molecules (in triplet state) or ions with two unpaired electrons (NiII),

i.e., S = S1 + S2 = 1 and hence Ms = –1, 0, +1. The total quantum number S is the sum of

the spin quantum numbers of the unpaired electrons. There are three possible cases,

Case (i) D = 0

In the absence of ZFS, the two possible transitions are expected, 0 → +1, –1 →

0 with the selection rule (Δms = ±1). These two are degenerate and hence only one

signal is observed in the EPR spectrum (Fig. 2A).

Case (ii) D > 0

34 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 Here, the zero-splitting removes the degeneracy in Ms as shown in Fig. 2B.

Furthermore, splitting occurs by the applied magnetic field. The two resulting

transitions are not now degenerate. Hence, two peaks are observed in the spectrum

when ZFS exists.

Case (iii) D >> 0

When spin-orbit coupling is large resulting in strong ZFS, the energy level

splitting diagram for the triplet state, 3A2g of Ni2+ (d8 ion with t02g e1g) in an octahedral

field is shown in Fig. 2C. There are no EPR transitions observed under normal

conditions because the transition (hυ1) energy is very much greater than MW energy.

The peak (hυ2) is also forbidden transition (ΔMs = ±2).

Odd Number of Unpaired Electrons

Consider, Mn(II) (d5) there are five odd number of unpaired electrons and

hence it exhibits Kramer’s degeneracy. The term symbol for the free ion ground state

is 6S. The ZFS produces three doubly degenerate spin states (Ms = ±5/2, ±3/2, ±1/2)

(Kramer’s degeneracy).

Each of these is split into two singlets by the applied field, producing six

levels. Hence, five transitions (–5/2 → –3/2, –3/2 → –1/2, –1/2 → 1/2, ½ → 3/2, 3/2 →

5/2) are expected and called fine splitting / structure.

The spectrum is further complicated by the hyperfine splitting due to the

manganese nucleus (I = 5/2). Thus, five peaks each further split into six hyperfine

components with equal intensities are expected and called hyperfine splitting.

The Mn2+ (d5) have a spherically symmetric electron distribution, so the 6S

ground state is not largely split by the crystal field, but mainly due to ZFS.

Effective Spin, S'

35 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 For an odd number of unpaired electrons, Kramer’s degeneracy leaves the

lowest spin state doubly degenerate (Ms = ±1/2). If the ZFS is large, this lowest

doublet will be isolated from the higher lying doublets (Fig. 1, right). Transitions will

then be observed only in the low-lying doublet, and hence the effective spin will

appear to have a value of only 1/2 (S' = 1/2).

An example is high-spin Co2+ (d7) with three unpaired electrons, i.e., S = 3/2

(Ms = ±3/2, ±1/2). The cubic field leaves a 4F ground state which, as a result of lower

symmetry crystal fields and spin-orbit coupling gives two doublets. The lowest

doublet (Ms = ±1/2) is separated from the next (Ms = ±3/2) by about 200 cm–1. Thus,

the effective spin has a value of 1/2 (S' = 1/2) instead of 3/2 (S = 3/2).

Forbidden Transitions

In V3+ (d2) triplet state the magnitude of the ZFS exceeds the energies of usual

EPR transitions (Fig. 2C). When this happens, it is not possible to observe EPR

transitions with Δms = ±1, but it has been possible to observe a weak transition

corresponding to Δms = 2, i.e., between the ms = ±1 levels. This line was further split

into eight components due to hyperfine splitting because I = 7/2 for V51.

Theory and Principle of NQR spectroscopy

NQR is a chemical analysis technique related to NMR. Unlike NMR, NQR

transitions of nuclei can be detected in the absence of a magnetic field and for this

reason NQR spectroscopy is referred to as "zero Field NMR. NQR is used to detect

atoms whose nuclei have a nuclear quadrupole moment.

In NQR, nuclei with spin ≥ 1, such as 14N, 35Cl and 63Cu, also have an electric

quadrupole moment so that their energies are split by an electric field gradient,

created by the electronic bonds in the local environment.

Principle

36 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 Any nucleus with more than one unpaired nuclear particle (protons or

neutrons) will have a charge distribution which results in an electric quadrupole

moment. Allowed nuclear energy levels are shifted unequally due to the interaction

of the nuclear charge with an electric field gradient supplied by the non-uniform

distribution of electron density (e.g. from bonding electrons) and/or surrounding

ions. The quadrupole moment can be positive or negative, depending on the shape

of the nucleus.

(Nuclear spins with I ≥ 1 having positive and negative quadrupole moments)

Unlike the NMR case, NQR absorption takes place in the absence of an external

magnetic field. Apply of the external static field to a nucleus splits the quadrupole

levels. Due to symmetry, the shifts become averaged to zero in the liquid phase, so

NQR spectra can only be measured for solids.

Orbital Symmetry

Unlike NMR where a powerful external magnetic field is needed, quadrupole

resonance takes advantage of a material´s natural electric field gradient. The

electrical gradients are available within certain asymmetrical atomic nuclei. These

gradients are due to the distribution of the electrical charge.

37 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 The electric quadrupole moments arise when the distribution of positive

electric charge in the nucleus is not perfectly spherical.

For example, a slightly oblate (pumpkin-like) distribution of positive charge

(left) can be thought of as the sum of a quadrupole distribution (centre) and a

spherical distribution (right).

Electric-Field Gradient

The inherent electric quadrupole moment and the electric-field gradient of the

nucleus create different energy states. This is analogous to the multiple energy states

in NMR.

In NQR, the required electric field (or the required electric-field gradient)

comes free, (a) the local arrangement of electrons around the nucleus; (b) that

arrangement, depends not only on the nature of the atom but also on its chemical

environment. This feature accounts for one of the benefits of NQR.

Any nucleus with more than one unpaired nuclear particle (protons or

neutrons) will have a quadrupole charge distribution. The NQR effect results from

the interaction of this quadrupole with an electric field gradient supplied by the non-

uniform distribution electron density (from bonding electrons). So the technique is

very sensitive to the nature of the bonding around the nucleus.

Spinning nuclear charge has electric field, extends outside nucleus. Interacts

with non-spherical (asymmetric) charge distribution caused by,

Non-bonding electrons (lone pairs, p, d)



38 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 Bonding electrons

Low symmetry environment, charges on neighbouring ions

So nucleus orients in certain quantized directions with respect to this field,

with different energy.

Energy levels and selection rules

In a liquid sample, molecular motion causes the electric field gradient to

average to zero and NQR is observed only in solid samples. 14

N and 35Cl are the

common nuclei which exhibit NQR absorption in the frequency range of 20 – 40

MHz.

For axially symmetric systems, the quantized energy levels due to the

quadrupole-electric field gradient interaction are

Em = e2 q Q [3 m2 – I ( I + 1) / 2 I ( 2 I -1 )]

In the above equation, I is the nuclear spin quantum number, q = ∂2V/ ∂z2, the

electric field gradient in the direction of the axis of symmetry and m, the projection

of I is given by

m = I, I - 1, …… - I + 1, - I

Note that the energy levels depends on m2 and +m and –m values correspond

to the same energy.

(a) Integer Spins

There are only four known stable nuclei with integer spin: 2H, 6Li, and 14N all

with I = 1, and 10B with I = 3. In addition there are some very long-lived radioactive

isotopes, such as 50V, with I = 6 and 138La with I = 5. Deuterium (2H) and 6Li have very

small electric quadrupole moments, so the NQR observation is difficult.

39 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

(b) Spin 3/2

Much of the NQR work in the literature is for spin 3/2 nuclei, which have two

doubly degenerate energy levels

(c) Other Half-Integer Spins

The results of numerical computations for half-integer spins 5/2, 7/2, and 9/2

are shown in below,

(NQR transition frequencies for spins 5/2, 7/2, and 9/2, the dashed lines are weaker transitions,

which are forbidden when η = 0)

40 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 The levels are labeled according to the largest component of the

wavefunction, though m is only a good quantum number when η = 0. In addition,

when η ≠ 0 all possible transitions are extremely weak. The dotted lines in the above

figure indicates that weaker transitions, which are not allowed at all when η = 0 but

which may be usable for large η.

The selection rule for an NQR transition is,

Δm=±1

The frequency for a transition from m - 1 to m level is given by

υ = *(3e2qQ)/4I (2J - 1)h] (2|m|-1)

where, the quantity e2qQ is called the nuclear quadrupole coupling constant.

For non-axially symmetric systems, the energy levels deviate further and the

degeneracy of the m ≠ 0 levels is split. The energy levels are then expressed in terms

of an asymmetry parameter η = (qxx - qyy)/qzz. In the NQR Spectrometer, the sample is

placed in an inductance, L, which is tuned to the absorption frequency by varying

the capacitance of the capacitors C, connected to L. The voltage output which is

affected by the absorption is observed in an oscilloscope.

NQR cannot be used as widely as NMR because of fewer I ≥1 nuclei and the

requirement of the solid state sample. However for compounds containing N and Cl,

good use of NQR has been made to generate the molecular data for e2qQ and η in

different environments. In metal cyano complexes, the migration of the electrons of

the central metal to the empty π* orbitals of the cyano groups affects the field

41 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

gradient values at 14N. In the case of group III trihalides, the terminal halides in

dimerised AlX3 have different frequencies than the bridging halides.

(Structure of AlBr3 dimer, the terminal bromines absorbs at 113.79 and 115.45 MHz, while bridging

bromines absorb at 97.945 MHz, Chlorides of I, Au and Ga absorb at lower frequencies)

The group frequencies of C-Cl can be used as an analytical tool. Values of C-

Cl absorption frequencies in MHz for some groups are –COCl (29 - 34), O-C-Cl (19.7

to 32.7), C-Cl (31 - 43), CCl2 (34.5 - 42.5), CCl3 (38 - 42), S-C-Cl (33 to 34.6) and = C-Cl

(36.5 to 39.5). Intermolecular hydrogen bonding reduces the field gradients at nuclei

such as 35Cl and 14N by about 20% and this can be detected in NQR.

Applications of NQR spectra

1. Molecular-structure determination and chemical analysis

For example, consider a chlorine atom bonded to carbon. The size of the

quadrupole coupling constant is roughly proportional to the p character of the C-Clσ

bond, and the value of the asymmetry parameter is proportional to the fractional π

character of the bond. The ionic character or polarity of the C-Cl bond is related to its

p character.

If the chlorine atom tends toward Cl- , its valence shell becomes more

symmetrical and the p character decreases. Thus, eQq decreases when

electropositive, charge-releasing substituents such as CH3 are present.

Electronegative substituents such as chlorine have the opposite effect. The π

electrons present to some degree in the C-Cl bond when the carbon atom is

42 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

unsaturated remove the axial symmetry, and η is found to be nonzero. Fortunately,

most C-Cl bonds have low asymmetry, and η can be set equal to zero.

The NQR frequency (and coupling constant) decreases steadily through the

series CH3Cl, CH3CH2Cl, (CH3)2CHC1, (CH3)3CCl. Each extra electropositive CH3

group increases the ionic character of the C-CI bond. This tendency parallels the

well-known increase in rate of chemical reactions which break the C-CI bond.

(a) 1,2,3,4,5,6-hexachlorocyclohexane

There are several stereo isomers with this formula which are of major interest

to pesticide chemists. The below figures show the NQR spectra of β (a) and γ (b)

isomers. The single resonance of the β isomer indicates that all six chlorines have an

identical environment and the assignment is that, they are all in equatorial position.

On the other hand, the γ isomer (lindane) shows four well-separated lines, the

two inner lines being twice the intensity of the outer pair. The number and intensity

of resonances, combined with a comparison of the actual frequencies found in other

molecules of known structure.

(a) (b)

(b) 2,4-dichlorobenzotrichloride

43 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 The spectrum of 2,4-dichlorobenzotrichloride shows two groups of four well-

separated transitions. The low-frequency group belongs to the less abundant Cl

37

nuclei. Starting at the left-hand (low-frequency) end of the 35Cl group, the first two

lines are assigned to the para and ortho chlorines, respectively. The CCl3 group does

not give a single line with triple intensity. Instead, the two lines, one twice as strong

as the other, indicate that the rotation of the CCl3 group is sterically hindered by the

presence of the ortho chlorine. In addition, the spectrum shows that NQR spectra

can give isotope-abundance information.

(c) Hexamethylenetetramine

The below figure shows the single resonance obtained at room temperature

from about hexamethylenetetramine, C6H12N4. This compound gives a strong signal,

and the single line indicates that the asymmetry parameter is zero, in agreement

with the known molecular structure.

Nitrogen atoms are found in a variety of different bonding situations: three

single bonds; one single, one double; triple bond (cyanide); isocyanide; conjugated

heterocyclic rings. Each type has characteristic frequencies.

44 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

(d) Bulk Explosives Detection Methods

When a low-intensity RF signal of the correct frequency is applied to the

explosive, usually in the range 0.5 to 6 MHz, the energy state of some of the 14
N

nuclei can be altered.

After the RF stimulation is removed, the nuclei can return to their original

state, releasing energy and producing a characteristic radio signal. The signal can be

detected using a special radio receiver and be measured for analysis of the

compounds present.

University Questions

1. What is “g” Factor? Explain the significance of “g” value in ESR spectroscopy.

What are the factors which influence the value of “g”? Discuss.

2. Explain the basic principle of NQR spectroscopy.

3. Predict the number of ESR lines for the following: (i) Ethyl radical and (ii)

Naphthalene radical.

4. Discuss the applications of NQR spectroscopy

5. Discuss the fine structure of ESR spectrum of a triplet state with two unpaired

electrons.

6. Write elaborate notes on the application of nuclear quadrupole resonance

spectroscopy.

7. Notes on double resonance in ESR.

8. Explain the g–factors and hyperfine splitting.

45 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)

 9. Discuss the effect of magnetic field on NQR spectra.

10. Explain the theory of EPR spectroscopy

11. Explain the principle of NQR spectroscopy.

12. (i) ESR spectrum of the complex ion [Mo(CN)8]3- in solution consists of one

line. If the sample is enriched with 13C, the spectrum consists of nine lines.

Explain the fact [Answer: This can be explained on the basis that Mo(V) in the

complex has d1 configuration and only a single line spectral is expected. But for the
13
C – enriched sample (for 13C, I = 1/2), there will be 2nI+1 or nine lines (Since 8

carbon atoms surround a molybdenum ion)]; (ii) Predict the number of lines in the

ESR spectrum of para- benzosemiquinone.

13. Indicate the number of resonance lines expected for the following nuclei

under the conditions given,

I (I = 5/2); η = 0; H0 = 0

N14 (I = 1); η = 0; H0 = 0

As75 (I = 3/2); η = 0; H0 = 0

Sb121 (I = 5/2); η = 1; H0 = 0

14. (i) Why water and alcohol are not suitable solvents for ESR studies? [Answer:

Water, alcohol and other high dielectric constant solvents are not used because they

strongly absorb microwave power]; (ii) Vanadyl acetylacetonate (VO+) shows

eight lines in the hyperfine structure of its ESR spectrum. Calculate the spin of

the V51 nucleus.

15. Calculate the frequency for an unpaired electron in a magnetic field of

strength 0.35 T (g = 2, β = 9.273 × 10-24 JT-1).

46 | P a g e NMCP – DEPARTMENT OF CHEMISTRY (PG)