Vibration-rotation spectra

• A diatomic molecule has rotational energy separations of ~1-10cm-1 and,

vibrational energy separations of ~3000 cm-1

• Consider a diatomic molecule that can execute rotations and vibrations

independently

• Although the Born-Oppenheimer approximation strictly includes electronic

energies, the combined rotational-vibrational energy is simply the sum of the
separate energies
Etotal = Erot + Evib
𝟏 𝟏 𝟐
Etotal = BJ(J+1) + 𝒗 + ῡ𝒆 − 𝒗 + ῡ𝒆 χ𝒆 cm-1
𝟐 𝟐

ῡ𝒆 may also be denoted as ωe

Vibration-rotation spectra
Vibration-rotation spectra
Selection rule: v= ±1, 2, etc., J = ±1
Vibration-rotation spectra

• Using a single prime for the upper state and a double for the lower state
is conventional in all branches of spectroscopy
• Consider, v = 0 to v = 1 transition:

• The rotational constant B is taken as the same for both upper and lower
vibrational states due to the Born Oppenheimer approximation: rotation
is unaffected by vibrational changes
Vibration-rotation spectra

• Using a single prime for the upper state and a double for the lower state is
conventional in all branches of spectroscopy

• ω0 is band origin and equally spaced lines (2B) on either side

• Lines to the low frequency of band origin (negative m, J = -1) are called P
lines, and to the higher frequency (positive m,  J = +1) are called R lines
Vibration-rotation spectra
Raman vs IR

• Raman: easier and faster sample preparation

• Molecules without a dipole moment can also be studied using Raman
• Water as solvent: water has intense absorption of IR and can’t be used.
Water is a weak Raman scatterer, and aqueous samples may be analyzed
• Raman spectroscopy allows for label-free detection of biological samples
• Glass vials can be used (unlike in infrared spectroscopy, where the glass
causes interference)
Electronic spectroscopy

• Studies the transitions between electronic states in a molecule

• Often between the HOMO and LUMO (BMO/ABMO)

• Also called UV/Vis spectroscopy

• Born-Oppenheimer approximation

Etotal = Evib + Erot + Eele

Etotal = Evib + Erot + Eelec

Electronic spectroscopy

• Vibrational changes will produce a 'coarse structure' and rotational

changes a 'fine structure' on the spectra of electronic transitions
• All molecules give electronic spectra since changes in the electron
distribution in a molecule are always accompanied by a dipole change

Vibrational Coarse Structure

• In the absence of rotational transitions, BO approximation may be written as

Vibrational Coarse Structure
Vibrational Coarse Structure

• No selection rule for v when a molecule undergoes an electronic

transition, i.e. every transition v" → v' has same probability
• Consider the electronic ground state where the majority of molecules are
at v" = 0
• The transitions will be (v', v") (0, O), (1, O), (2, O), etc.
• Forms a band since, under low resolution, each line of the set appears
somewhat broad and diffuse
• The diagram shows that the lines in a band crowd together more closely
at high frequencies; this is a direct consequence of the anharmonicity of
the upper state vibration, which causes the excited vibrational levels to
converge
Vibrational Coarse Structure

• Spectrum gives the values of the vibrational frequency and anharmonicity constant in
the ground state and the excited state
• This latter information is particularly valuable as it gauges the bond strength of such
species
Morse curve: potential energy change
• Morse curve represents the energy when one atom is considered fixed on
the r = 0 axis, and the other is allowed to oscillate between the limits
• For v = 0, the atom is most likely to be found at the centre of its motion, i.e.
at the equilibrium internuclear distance re, For v = 1, 2, 3, . . . the most
probable positions steadily approach the extremities
Franck-Condon Principle

• All vibrational transitions in an electronic spectrum are equally probable

• However, the intensities of the lines arising from these transitions are not the same

• Given by the Franck-Condon principle

• According to the Franck-Condon principle, electronic transition takes place so

rapidly that a vibrating molecule does not change its internuclear distance

appreciably during the transition

• Franck-Condon principle suggests that a transition occurs vertically on the

potential energy diagrams of the ground state and the excited state
Franck-Condon Principle
Sigma, pi and non-bonding orbitals
Sigma, pi and non-bonding orbitals
Electronic transitions
Electronic transitions
Electronic transitions

The four p atomic orbitals combine

to form four pi molecular orbitals (2
bonding and 2 antibonding) of
increasing energy

Delocalization

The conjugated diene is lower in energy, thus more stable as

conjugated pi bonds are more stable than isolated pi bonds
Electronic transitions

• With increase in conjugation, the energy gap for a π - π* transition becomes

increasingly lower, and the wavelength of light absorbed correspondingly
becomes longer
• The absorbance due to the π - π* transition in 1,3,5-hexatriene is at 258 nm,
corresponding to a ΔE of 111 kcal/mol in contrast to
Selection rules
• Spin selection rule
• The Spin Selection Rule forbids transitions between states with different total
spin and thus different spin multiplicity. This rule allows transitions only between
states with the same total intrinsic spin ( ΔS=0 ) and, thus, the same spin
multiplicity value in the term symbol. In other words, the direction of the
promoted electron's spin should not change

• The Laporte Selection Rule applies to molecules with a center of symmetry

• This rule forbids transitions between states with the same parity (symmetry) with
respect to an inversion center
• Parity is indicated on molecular orbitals and term symbols with subscripts g
(gerade, or even) and u (ungerade, or uneven)
• Transitions between u and g terms are allowed but those between two g or two
u terms are forbidden
NMR spectroscopy

• Nuclear Magnetic Resonance Spectroscopy

• 1945: Bloch, Hansen, and Packard at Stanford (signal from protons in water)
• 1945: Purcell, Torrey, and Pound at Harvard (signal from protons in paraffin)
• 1950: Bloch and Purcell, Nobel Prize in Physics
• 1953: First commercial NMR spectrometer
• 1H NMR, 13C NMR, 31P NMR, 71Ga NMR, etc.

“Spin is a highly abstract concept, which may never be

entirely ‘grasped’ beyond knowing how to manipulate
the quantum mechanical equations.” – Adam Levitt
NMR spectroscopy
• Fundamental property of a nucleus: nuclear spin
• Any unpaired electron, proton, or neutron will possess a spin of ½
• Atomic nuclei, which are composed of protons and neutrons, may also
possess spin

Mass number Atomic Nuclear spin (I)

number
Odd Even or odd 1/2, 3/2, 5/2
Even Even 0
Even Odd 1, 2 , 3

• A spinning nuclei generates a magnetic field of magnetic moment μ

𝜸𝑰𝒉
𝝁=
𝟐𝝅
• γ is a constant called magnetogyric ratio and I is the nuclear spin
NMR spectroscopy

• When an external magnetic field is applied, nuclear moments orient

themselves in specific orientations with respect to the field
• A nuclei of spin I will have 2I+1 orientations, given by the values of the
magnetic quantum number mI (-I to +I)
• mI specifies the z-axis component of the spin angular momentum for a
particle having spin quantum number s
• The energy of interaction between the two fields is given by

𝜸𝒉
𝑬=− 𝒎𝑩
𝟐𝝅 𝑰
NMR spectroscopy

• Selection rule for NMR transitions: mI = ±1

• Transition energy is thus given by

γ𝒉𝑩
𝑬 =
𝟐π
• Fundamental resonance condition

𝜸𝒉𝑩 𝜸𝑩
𝑬 = 𝒉𝝂 = ; 𝝂= (frequency in RF region)
𝟐𝝅 𝟐𝝅
NMR spectroscopy

Relaxation time: Relaxation time in NMR is the time it takes for a system
to relax, repopulating the ground state (milliseconds to minutes)
NMR spectroscopy
• The data acquired at the NMR spectrometer is called free induction decay
(FID), which is the combined decay of nuclear spins from various molecules
present in the analyzed sample after excitation with a short radio-frequency
pulse
• FID data is a sine/cosine wave in the time domain and the signal decays
exponentially toward zero
• The time domain signal is processed by Fourier transformation (FT) to be
expressed as a frequency domain spectrum
Chemical shift: NMR spectroscopy
• The different local chemical environments surrounding nuclei cause
them to resonate at slightly different frequencies
• Caused by a change in electron density around a nucleus, such as a
bond to an electronegative group
• Frequency shifts are minuscule compared to the fundamental NMR
frequency (Hz vs MHz)
• For this reason, chemical shifts (δ) are described by the unit ppm
Shielding and deshielding
Peak multiplcity
• Peak multiplicity in NMR spectroscopy measures the number of neighboring
hydrogens for a specific proton atom or group of atoms.

• For a proton with n neighboring hydrogens, peak multiplicity is given by n + 1

Methanol
NMR spectra
NMR spectra
NMR spectra
NMR spectroscopy
ESR (EPR) spectroscopy

• Electron paramagnetic resonance (EPR) or electron spin

resonance (ESR)
• For studying materials that have unpaired electrons
• Principle: analogous to NMR, deals with electron spins rather than
nuclear spins
• For studying metal complexes, free radicals, transition metal ions,
ions and molecules having an odd number of electrons, and
organic radicals
ESR (EPR) spectroscopy

• Electrons have spin and orbital angular momentum

• The magnetic moment of the electron can align either parallel to or
antiparallel to the external magnetic field

𝑬 = 𝒈𝒆 𝝁𝑩 𝑩𝟎

g factor: describes the relationship

between the magnetic field and the
energy levels of unpaired electron
μB: Bohr Magneton (measure of
electron’s magnetic field)
B0: strength of the external magnetic
field
Resonance condition and hyperfine splitting

• An unpaired electron can change its electron spin by either

absorbing or emitting a photon

• Resonance condition: 𝒉𝝂 = 𝒈𝒆 𝝁𝑩 𝑩𝟎
• In the microwave region (9–10 GHz) region, for a magnetic field of
strength 0.35 T
• Hyperfine splitting in ESR: caused by the interaction of electron
spins with the magnetic nuclei in the sample
• A magnetic nucleus with quantum number I will split a single ESR
line into 2I+1 lines (peaks)
Resonance condition and hyperfine splitting
ESR vs NMR
ESR spectroscopy: applications

• To study the role of free radicals in

oxidative stress
• For the detection and identification of
free radicals
NQR Spectroscopy

• Nuclear Quadrupole Resonance (NQR) spectroscopy

• Also known as "zero Field NMR“
• Used to characterize chemical compounds containing quadrupolar
nuclei
• Just like NMR, NQR uses radio-frequency to detect transitions between
sublevels of a nuclear ground state
• NMR: sublevel energy splitting is due to a nuclear interaction with an
applied magnetic field
• NQR: predominant splitting is due to an interaction with electric field
gradients within the material
NQR Spectroscopy

• Nuclei with a spin quantum number I ⩾ 1 possess an electric quadrupole

moment
• This is a mathematical way of saying that the nucleus acts as if its charge
distribution were nonspherical
• If the electric field at the nucleus is not uniform, then the energy of the
nucleus will be different in different orientations
• In other words, the nuclear quadrupole moment interacts with the
electric field gradient at the nucleus
NQR Spectroscopy

• When both quadrupolar and magnetic field interactions are present, the
spectroscopy that results depends on the relative size of the Zeeman and
quadrupole terms
• If the Zeeman dominates, NMR results
• In the case of zero, or very small, magnetic field, NQR results
• In both cases, we observe transitions between quantized levels of the
nuclear spin angular momentum the difference is the interaction that
splits these levels
 Mössbauer spectroscopy

• Used to study changes in nuclear structure with

the absorption and re-emission of gamma rays
• The technique uses the Mössbauer effect to
probe the transitions between the excited and
ground states of the nucleus
• Mössbauer spectroscopy requires the use of
solids or crystals that have a probability of
absorbing the photon in a “recoilless” manner
• The most studied isotope is 57Fe
Mössbauer Effect
• Conservation of momentum requires the nucleus to recoil during the
emission or absorption of a gamma ray
• For a nucleus at rest to absorb a gamma ray, the gamma ray's energy
must be greater than the energy gap to account for the loss due to recoil
• Recoil energy depends inversely on the mass of the system
• The solid or crystal absorbs the energy as phonons
• There is a probability that no phonons are created, and the whole lattice
acts as the mass, resulting in a recoilless emission of the gamma-ray
• The new radiation can excite the next ground-state nucleus
• The probability of recoilless events increases with decreasing transition
energy
Mössbauer Spectroscopy

• A solid sample is exposed to a beam of gamma radiation

• A detector measures the intensity of the transmitted beam
• The atoms in the source emitting the gamma rays and those absorbing
are the same
• If the emitting and absorbing nuclei are in identical chemical
environments, it leads to resonant absorption
• The difference in chemical environments causes the nuclear energy
levels to shift
• To bring the two nuclei back into resonance, a change in the energy of
the gamma-ray is necessary
Mössbauer Spectroscopy

• Conditions for Mössbauer active nuclei

• A small energy gap between the ground and excited states; gamma
rays at higher energy are not absorbed in a recoil-free manner, and
resonance only occurs for gamma rays of low energy
• The resolution of Mössbauer spectroscopy depends upon the
lifetime of the excited state: the longer the excited state, better the
resolution