Atomic Structure & Spectra

Rutherford Atom Model

• It was more or less accepted by the end of 19 th century that all the matter is
composed of tiny indivisible particles called atoms.
• It was known that electrons generated from the atoms and they are negatively
charged. Since the atom must be neutral, it was imagined that the atom must be
composed of both these charges.
• J. J. Thomson in 1898 proposed a plum-pudding model which states that the
atoms are positive lumps of matter in which electrons are embedded as the raisins
are present in a fruitcake.
• Between 1908 and 1913, Hans Geiger and Ernest Marsden performed
experiments to determine the structure of the atom based on suggestions by
Ernest Rutherford.
• They used a collimated beam of alpha particles (charge ), which is the nucleus
of helium atom.
• The alpha particles have a mass nearly 8000 times that of an electron and
velocities of the order of 107 m/s.
• They used a gold-foil as the target and a ZnS screen with a microscope as a
detector.
• When charged particles hit the ZnS screen, light flashes appear on the screen
which can be observed with a microscope.

• If the plum-pudding model is to be correct, the alpha particles must pierce through
the atoms without getting any substantial deviation.
• However, as Rutherford stated “It was as incredible as if you fired a 15-inch shell at
a piece of tissue paper and it came back and hit you.”
 a piece of tissue paper and it came back and hit you.”
• Rutherford, based on the observations, proposed that:
○ the positive charge in an atom is concentrated in a tiny region (nucleus) and
that constitutes the entire mass of the atom.
○ the electrons are uniformly distributed around the nucleus within a spherical
volume.
• The atom in this sense is nearly empty space. Proton size is of the order of
0.84-0.87 fm, whereas the electron size is found to be of the order of 10 -22 m (If the
diameter of proton is of the size of a mustard seed (~ 1 mm), electron will be
revolving around it in an orbit at a distance as big as the radius of a cricket
stadium). Whenever the alpha particles make close encounter with the nucleus
gets deflected away strongly due to electrostatic repulsion.
• The amount of deflection depends on the charge of the nucleus. Thus, by using
different target atoms, one can get an estimate of the charge of the nucleus by
analyzing the scattered alpha particles.
• The charge of the nuclei turned out to be an integral multiple ( ) of . This
number is referred to as the atomic number, which is the number of protons in
the nucleus.
• The Rutherford scattering formula yields the number of particles per unit area
that reach the screen at an angle :
,

where
is the total number of particles that reach the screen,
is the total number of atoms per unit volume in the foil,
is the atomic number of the foil atoms,
is the distance of screen from the foil,
is the initial kinetic energy of the alpha particles, and
is the foil thickness.
• Since varies as , the number of particles scattered at angles
more than is quite small ( ).
• The predictions of the scattering formula agreed with the experimental
observations and Rutherford is credited with the discovery of nucleus.
• An particle can make its closest approach to the nucleus in a head-on collision
followed by scattering at 180°.
• Let R be the closest approach at which the kinetic energy of the particle is totally
converted into the potential energy. Thus,
 converted into the potential energy. Thus,

• Kinetic energy maximum of the alpha particles of natural origin is 7.7 MeV. The
atomic number of gold is 79. Substituting these values and one gets
m. (Published value: 5.44 fm , Ref: https://paperpile.com/shared/T6eobN)
• Let us consider the planetary model of hydrogen atom as proposed by Rutherford.
Assume that an electron of charge is revolving around a proton of charge in
a circular orbit of radius .
• The centripetal force holding the electron in an orbit of radius is
provided by the attractive potential of the nucleus: .
• The electron velocity is then given by .
• The total energy .
• Substituting the value of , one obtains .
• The total energy is negative, meaning that the electron is bound to the nucleus.
• A major problem with the planetary model of atoms is that it fails to explain the
stability of atoms.
• A revolving electron is an accelerating charge which in turn should emit
electromagnetic radiation according to classical electromagnetic theory. Thus, the
electron would lose energy continuously and spiral into the nucleus within a
fraction of a second.

Atomic Spectra

• Blackbody radiation is the radiation emitted by material bodies. This emission

consists of almost every sort of wavelengths with different intensities as described
by Planck's radiation formula.
• This emission corresponds to emission of the electromagnetic radiation by the
variety of atoms present in the material. In addition, these atoms are in condensed
phase (solid or liquid) where we see a collective behavior.
• If we have only one sort of atoms in the gas phase where there is no interaction
between the atoms by themselves, the emission of light happens to be
characteristic of the atom under concern.
• Spectrum Demo: Continuous and Emission
• The emission occurs when the atoms are excited either by electrical discharge or
by other means.
• The emitted light displayed as a function of wavelength or frequency is referred to
as an emission spectrum.
• If a white light (which consists of a continuum of wavelengths) is sent through an
atomic or molecular gas, one can see dark lines that result in the spectrum of the
light that emerges through the gas. This is referred to as an absorption spectrum.

• The spectrum of the Sun has dark lines because, the luminous part of the Sun
emits all the wavelengths similar to that of a perfect blackbody (5800 K), and the
cold gas in the outer envelope of the Sun absorbs radiation characteristics of the
atoms present in it.
• The number, intensity, and the exact wavelengths of the lines depend on the
temperature, pressure, the presence of electric and magnetic fields, and the
motion of the source. By analyzing the spectrum, one can tell which elements the
atmosphere contains, whether they are ionized, and whether the star is moving
toward or away from us.
• The spectroscope was invented by Fraunhofer (1814), who discovered that the
continuous spectrum of the Sun is riddled with dark lines, which are now referred
 continuous spectrum of the Sun is riddled with dark lines, which are now referred
to as Fraunhofer lines.

• A Swiss school teacher Johann Balmer in 1885 noticed that the four prominent
lines of atomic hydrogen (6563 Å, 4861 Å, 4340 Å, 4102 Å) could be represented
by a simple relationship:
Å, where takes values 3, 4, 5, and 6.

• The series represent what is known as Balmer series today.

• In terms of the wave number , the above equation may be written as
• in cm-1 with cm-1, which is called the Rydberg

constant.
• After Balmer, it was realized that the series did not stop at , but continued till
the converging frequency of .
• It was also noticed that there are other series with replaced by an integer (= 1,
2, 3, … with ):
• in cm-1 with cm-1.

• This equation defines the entire hydrogen emission spectrum. However, the
occurrence of such a series remained a mystery until Niels Bohr came up with a
model of hydrogen atom.

Bohr Atom Model

• Bohr made two bold (but unjustifiable) assumptions (1913)!

○ The electrons in a hydrogen atom revolves around the nucleus just as the
planets revolve around the Sun - Planetary model of the atom.
○ The magnitude of the angular momentum in each of these orbits is restricted
to integer values (angular momentum is quantized):

, (1)
 , (1)

where and .
• Once these assumptions are taken for granted, the angular momentum of an
electron in a circular orbit:

(2)

Or,

(3)

• The centripetal force is provided by the electrostatic attraction:

. (4)

• Substituting the value of on the RHS, and solving for (which now depends on
), we get
, . (5)

• Thus, we see that electrons cannot revolve around the nuclei in any arbitrary
radius, but their location is quantized in space. This is referred to as space
quantization!
• The smallest radius corresponds to , for which and is called
the Bohr radius .
• Thus, .
• The energy of hydrogen atom obtained in Rutherford atom model is

(6)

• Using the value of for , the energy of hydorgen is

, (7)

where , the ground state energy of hydrogen atom.

• Notice that hydrogen atom cannot have any arbitrary energy values - the energy
spectrum is said to be quantized.
• Justification for Bohr's idea of integral nature of angular momentum was
established once de Broglie proposed the idea of matter waves. Bohr's orbits now
seen to correspond to integral multiple of de Broglie wavelengths of electrons in a
hydrogen atom.
• Thus, the same results can be obtained by imposing the boundary condition that
the electron orbits are determined by the equation

, (8)

where corresponds to the de Broglie wavelength of the electron.

 where corresponds to the de Broglie wavelength of the electron.
• The de Broglie wavelength
• From eq. (4),

(9)

• Therefore,

(10)

• Now, using eq. (10) in eq. (8), we arrive at eq. (5).

• According to the Bohr model, an atom gets excited when photon energy gets
absorbed by the atom. Since the energy levels are discrete, only a discrete amount
of energy can be absorbed. An atom that absorbs a photon transitions to a higher
energy level and it said to be excited.
• Similarly, when an excited atom releases its extra energy (of course in discrete
manner depending on the available energy levels), a photon is emitted.
• The photon energy emitted in a transition is given by ( and refer to initial and
final states, respectively.)
.

• Expressing this in the units of :

,

where the Rydberg constant: .

• By choosing , one obtains the Balmer spectral series!
• The ionization energy of an atom is the minimum amount of energy required to
remove an electron from its ground state. For hydrogen, it is 13.6 eV.
 Lyman series: UV (1 .2 e 13. e )
Balmer Series: UV-Visible (1. e 3. e )
Paschen Series: Infrared (1.5 e . e )
Bracket and Pfund Series: Mid-IR – Far-IR

• Even though Bohr model could reproduce the spectral series of hydrogen atom, it
fails to describe atoms having multiple electrons. In addition, it could not explain
several finer spectral signatures of hydrogen atom.
• By introducing elliptical orbits instead of circular orbits, Sommerfeld was able to
explain some finer details in the spectra of hydrogen atom. However, in this case, it
could not explain spectra from any other atom.
• When a hydrogen atom is in a highly excited state, the radius at which the electron
orbits can be quite large. For example, a radius of 10 micron corresponds to
. Such atoms are called Rydberg atoms.
• The electronic energies are nearly continuous for an electron in a Rydberg atom,
and it essentially can radiate the same frequency ( , where E1 is in eV)
with which it revolves, consistent with the prediction of classical electromagnetic
theory. Thus, the greater the value of the quantum number, the more quantum
physics predictions approach those of classical physics. This principle is referred to
as Bohr's correspondance priniciple.
• Failures of Bohr's model of atom
○ It applies to only hydrogen(ic) atoms
○ Fine structure of hydrogen atoms cannot be explained
○ Cannot explain why some spectral lines are brighter than others
○ Cannot explain how atoms comine to form molecules and solids.