Prof.Dr.G.

Venkatachalam/PG-TRB/Chemistry/UNIT-IX/2025
Born-Oppenheimer Approximation
An isolated molecule in space has various forms of energy by virtue of its different kinds of
motion and intramolecular interactions. Consider different energies with reference to a diatomic
molecule. The molecule possesses translational energy by virtue of the motion of the molecule as a
whole. It may possess rotational energy due to bodily rotation of the molecule about an axis
perpendicular to the internuclear axis and passing through the centre of gravity of the molecule. The
molecule exhibits vibrational energy due to periodic displacement of its atoms from their
equilibrium positions. It also possesses electronic energy since the electrons associated with each
atom and bond are in constant motion. Electronic energy is associated with the transition of an
electron from the ground state energy level to an excited state energy level of the molecule due to
the absorption of a photon of suitable frequency. Further, the molecule exhibits nuclear energy and
energy due to nuclear and electron spins. As a first approximation, the total energy of a molecule
can be expressed as the sum of translational, rotational, vibrational, electron, spin and nuclear
energies viz.,

E total =E trans +E rot +E vib +E el +E spin +E nuclear. It is assumed that various types
energy associated with different motions of the molecule are independent of one another. A
molecule can have several levels of these different energies. The translational energy is not
quantized whereas all the energies are quantized. It means that a molecule can exist only in certain
discrete electronic, rotational, vibrational, spin and nuclear states. The separation between
electronic energy levels is usually much larger than those between vibrational energy levels which,
in turn are much larger than those between rotational levels which is much larger than spin energy
levels. Thus because of much difference in mass between the electron and the nucleus, it is
permissible as a very good approximation, to regard the respective motions as mechanically
separable. This simplification is usually referred to as the Born-Oppenheimer approximation. In
practice, it means that we need not consider electrons explicitly in the treatment of molecular
vibrations. However, the presence of electrons does make itself felt in the dependence of the force
constants on the electronic structure.
Furthermore, E el >>E vib >>E rot >>E trans
Since the translational energy is negligibly small, the Born-Oppenheimer approximation can
be written as E = E rot +E vib +E el
The time required for an electronic is about 10- 15 s and the energies involved are about 10 to
50 times greater than for a typical vibrational transition (10- 13 s). The rotational motion interacts
with the vibrational motion. However, the rotation-vibration interactions are generally very weak.
The energy involved in a typical rotational transition is about 103 times smaller in magnitude than in
a typical vibrational transition. Thus, separation of rotational motions from vibrational motions
represents a good approximation for vibrations of free molecules. The time required for a rotational
transition (about 10- 10 s) is higher than for a typical vibrational transition (10- 13 s).

Since the frequency of radiation absorbed or emitted depends on the energy difference
between the two levels involved in transition and this energy difference is different for rotational,
vibrational and electronic energies etc. The corresponding spectra consequently occur in different
regions of the electromagnetic spectrum.

RELAXATION TIME
This is an effective lifetime associated with the return of the molecule from the excited state
to the ground state. Generally, it is long if the energy gap is small but shorter if the energy gap is
larger. Relaxation times associated with high energy techniques like electronic and photoelectron
spectroscopy are relatively small while those associated with lower energy methods such as NMR
and microwave spectroscopy are correspondingly longer. The relaxation time defines only the
minimum width for the spectral line. Factors which depend on the environment and also on the
molecule or atom itself determine the relaxation times.
Doppler Effect
It arises when a molecule being investigated has a velocity relative to the observer or
observing instrument (detector). Doppler broadening is caused by the motion of the radiating atoms
as a result of thermal activity. According to the Doppler effect, the precise frequencies of radiations
which are absorbed or emitted by molecules (or atoms) depend on their component of velocity in
the direction of a radiation at the time of interaction. In liquids and gases, the motion of the
molecules causes their absorption and emission frequencies to show the Doppler shift.
 Different molecules will have different values of the observed frequency. Doppler effect
causes the radiation to effectively decrease the wavelength for those atoms which travel towards the
source and somewhat longer wavelengths are observed for atoms moving away from the source.
Since the motion of the gas and liquid phases is random, shift to both low and high frequencies
occur and hence Doppler broadening spectral line is obtained.

Lambert’s law:
When monochromatic light is allowed to pass through a transparent medium, the rate of
decrease in intensity with thickness of medium is directly proportional to the intensity of light. The
law may be expressed by the differential equation, -dI/dl = kI ; I is the intensity of incident light of
wavelength λ, l is the thickness of medium and k is a proportionality factor.
Beer’s law or Beer-Lambert Law:
Beer-Lambert Law, also known as Beer's Law, describes the relationship between the
absorption of light by a substance and its properties.
When a beam of monochromatic radiation of suitable frequency passes through a solution, it
is absorbed by the solution. As a result, the intensity of the light is considerably reduced. If I0 is the
intensity of the incident beam and It is the intensity of the transmitted beam, then the intensity of the
light absorbed, Ia is given by Ia = I0 -It
Intensity I absorbed by the sample is directly proportional to the concentration and thickness
of the absorbing solution. Mathematically, dI/I = -αcdx, where dI is the change in intensity
produced by the absorption of radiation on passing through a thickness dx of the solution of
concentration c and α is the proportionality constant. The minus sign indicates the reduction of
intensity. Integrating the above equation, ln I/I0 = 2.303log (I/I0) = -αbc
Thus, Beer-Lambert law states that the intensity of a beam of monochromatic radiation
decreases exponentially with increase in the thickness x and the concentration c of the absorbing
medium. Putting α/2.303 = ε and log (I0/I) as the absorbance, A of the solution, we get
A = log (I0/I) = εbc or εlc
ε is called the absorption coefficient or extinction coefficient of the absorbing medium. It is
characteristic of the solute and depends upon the nature of the solvent, temperature and the
wavelength of the radiation employed. If the concentration c is expressed in mol/dm -3 and the path
length b or l in cm, then ε (expressed as dm3 mol-1 cm-1) is referred to as molar absorption
coefficient or molar extinction coefficient. The transmittance T, is defined as T = I/I0
CW and FT-NMR

NMR instruments commonly encountered are continuous wave NMR spectrometer and
Fourier transform NMR spectrometer.

Continuous Wave (CW) NMR Spectrometer

CW-NMR spectrometer detects the resonance frequencies of nuclei in a sample placed in a

magnetic field by sweeping the frequency of radio-frequency (RF) radiation through a given range
and directly recording the intensity of absorption as a frequency. The spectrum is recorded and
plotted simultaneously with a recorder synchronized to the frequency of the RF source. The
important components of CW spectrometer are

(i) Magnet. The accuracy and quality of an NMR instrument depends upon the strength of the
magnet. Resolution increases with an increase in field strength provided the field is homogeneous
and reproducible. Magnets may be conventional type, permanent of electromagnets and super
conducting solenoids. The strength of magnetic field should be very high, i.e., 20000 G, because the
chemical shifts are proportional to the field strength. High resolution NMR has super-conducting
magnets with a H1 frequency of 470 MHz.

(ii) Field sweep generator. A set of Helmholtz coils located parallel to the magnet faces permits
alteration of the applied field over a small range. For a 60 MHz proton instrument, the sweep range
is 235 milligauss. For F19 and C13, sweeps as great as 10 KHz are needed.

(iii) Transmitter (radiofrequency source). A frequency of 60, 90 or 100 MHz is used in high
resolution NMR.

(iv) Recorder. The radiofrequency signal produced by resonating nuclei is detected by means of a
coil that surrounds the sample.

Fourier Transform NMR spectrometer

FT-NMR spectrometers consist of helium cooled super conducting magnets (solenoids) and
operate in the pulsed FT mode. The sample in a deuterated solvent is irradiated with strong pulse of
radiofrequency radiation. The nuclei absorb their appropriate frequencies from the pulse. The pulse
duration may be ≈ 10 μs and when it is switched off, the nuclei undergo relaxation processes and re-
emit the absorbed energies and coupling energies.

The output is digitized in a computer and each individual frequency is identified from the
interference pattern by the mathematics of Fourier transforms. The sensitivity of the instrument is
measured as the ratio between the signal intensity and the intensity of background noise on the
spectrum. FT is the mathematical operation required to convert a time domain spectrum into a
frequency domain spectrum and vice-versa.

An entire spectrum can be recorded, computerized and transformed in a few seconds.

Technically, very rapid. FT method gives refined spectra even at very low concentrations. The
signals are very clear with almost no electronic background noise. It can study nuclei with small
magnetic moments (C13, N15, O17). FT NMR technology is used in engineering, industry quality
control and medicine. Magnetic resonance imaging (MRI) is one of the most prominent FT-NMR
applications.
Saturation

When a nucleus is exposed to radiation of a suitable frequency, absorption takes place due to
slight excess of lower energy state nuclei that are present in the strong magnetic field. This excess is
small and so there is always a possibility that the absorption process will equalise the number of
nuclei in the two states. This causes the absorption signal to decrease and to approach zero. Under
these conditions the spin system is said to be saturated and the process is called saturation. In
order to prevent saturation, the rate of relaxation of excited nuclei to their lowest energy state must
be greater than the rate at which they absorb the radio frequency energy.

RELAXATION PROCESS

Relaxation processes involve non-radiative transitions by which a nucleus in an upper

transition state returns to the lower spin state. Types of relaxation processes are:

1. Spin-Lattice Relaxation or Longitudinal Relaxation.

The term lattice refers to the frame work of molecules containing the precessing nuclei.
Spin-lattice relaxation process, designated by the time T1, involves transfer of energy from the
excited protons to the surrounding protons that are tumbling at the appropriate frequencies.

Mechanism of spin-lattice relaxation involve, dipole-dipole relaxation, spin rotation

relaxation, quadrupolar relaxation, scalar coupling and chemical shift anisotropy.

2. Spin-spin Relaxation or Transverse Relaxation.

Spin-spin relaxation, characterized by the time T2, involves transfer of energy among the
precessing protons which results in dephasing, line broadening and signal loss. The term T2 is used
to denote the time for all the contributory factors to the transverse signal loss.

Spin-spin relaxation mechanisms can be induced by following processes. i) Dipole-dipole

interaction between the same type of nuclei having the same Larmor frequency and generate
magnetic field of correct frequency for relaxation. This process helps to destroy the phase
coherence and leads to transverse relaxation.

(ii) This process involves generation of slightly different magnetic fields due to magnetic
fields of nuclei whose motions are slow and lead to a variety of Larmor frequencies. This process is
important in viscous liquids or solids where the movement of nuclei is restricted.

3. Quadrupole Relaxation. It is the prominent relaxation process for nuclei having I>1/2.
Thus, the nuclei such as B11, N14, O17 etc. because of the anisotropic interaction between non-
spherical electrically quadrupole nuclei and the electric field gradients at the nucleus caused by the
electronic environments, possess an unsymmetric positive charge distribution on the nuclei. These
nuclei thus exhibit electric quadrupole moments and relax rapidly and display extremely broad
signals. This process of deactivation of nuclei is known as electric quadrupole relaxation. For
halogen nuclei (Cl2, Br2, I2) this mechanism is so fast that these nuclei, instead of having large
magnetic moments, are practically non-magnetic for the purpose of high-resolution NMR
spectroscopy. In case of N14 and H² quadrupole relaxation is less effective so that their resonance
lines can be observed more easily.
 The broadening of signal is directly proportional to the life time of the absorbing nuclei in
the excited state. More efficient the relaxation process, broader is the resonance band. Hence, for
maximum resolution

(i) Paramagnetic impurities like oxygen and magnetic ions should be avoided.

(ii) The use of solids or viscous samples should be avoided.

Bloch equations

The Bloch equations are fundamental to understanding and interpreting NMR and MRI
experiments. They are used to model the behaviour of spins in various magnetic resonance
techniques. They help in determining relaxation times (T1 and T2), which provide valuable
information about samples properties and environment. Bloch stated that most nuclei possess
inherent magnetic fields though too small to be observed in the ambient field of the earth. A minute
amount of energy is absorbed or emitted as the nuclei jump from one energy level to another. Thus,
as a result of the magnetic properties of nuclei arising from their axial spin, radio-frequency
radiation is absorbed in the magnetic field.
dMx/dt = y (MyBz – MzBy) – Mx/T2
dMy/dt = y (MzBx – MxBz) – My/T2
dMz/dt = y (MxBy – MyBx) – (Mz – M0)/T1
y is the gyromagnetic ratio; Mx, My and Mz are the magnetization components. Bx, By and Bz are
the components of the effective magnetic field in the rotating frame; M0 is the equilibrium
magnetization along the z-axis; T1 and T2 are the longitudinal and transverse relaxation times
respectively.