CHM 112M: Lecture 2

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Arnab Ghosh
August 14, 2023

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1 Bohr’s Atomic Theory of Hydrogen
Niels Bohr revolutionized atomic science in 1913 by applying quantum theory
to explain the hitherto mysterious optical spectrum of hydrogen and proposing

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a model that could predict the electronic structure of heavier atoms1 .
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Figure 1: Emission spectrum of Hydrogen (Adapted from PKG’s book).

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By the late 19th century, significant progress had been made in spectroscopic
techniques, allowing the observation of optical emission spectra for various
atomic species. One notable example is the emission spectrum of the hydro-
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gen atom as depicted in Fig. 1. The spectrum displays distinct lines that follow
a pattern and Johann Balmer, in 1885, proposed an empirical formula known
as the Balmer series to describe the pattern of lines in the visible spectrum of
the hydrogen atom
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1 1
ν̄ = RH − 2 ; RH = 1.09 × 107 m−1 and n = 3, 4, 5... (1)
22 n
1 Note: This is Brief Overview of Class Topics (For Internal Use): Not a Lecture Substitute.

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 Other series of lines were subsequently discovered in IR and UV regions (Fig. 1)
and the line energies were found to follow a general formula of a following type
 
1 1
ν̄ = RH − , (2)
n21 n22

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where, n1 and n2 are integers and for each series, n1 = 1, 2, 3... is fixed, and n2
varies, with the lowest value starting from n1 + 1. The empirical formulation
though evolved with time with number of views on probable atomic models, but
none of them were adequate to give a satisfactory answer to the observed line
spectra. It was Bohr who combined all these views and introduced a couple of
revolutionary assumptions on his own:

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1. Positively charged nucleus at the center of an atom (Rutherford).
2. Existence of stationary orbit that does not emit any radiation (Bohr).

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3. Energy and ang. mom. are quantized for electronic states (Nicholson).
4. Orbital angular momentum is given by L = n(h/2π) (Ehrenfest), where
n = 1, 2, ..., which Bohr called quantum number.
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5. Absorption or emission of energy takes place by single electron jump2
from one orbit to another (Conway) and the emitted or absorbed energy
of radiation is determined by the difference in energy between the two
stationary states involved in the transition, i.e., hν = E2 − E1 (Bohr).
and quantitatively explained the spectrum of hydrogen atom.
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Figure 2: Bohr’s model of H-atom (Adapted from PKG’s book).

2 Quantum jumps are experimentally realized only in 1988 by D. J. Wineland (2012 Physics

Nobel Prize).

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 1.1 Atomic spectra of Hydrogen
For the electron that moves in a stationary orbit of radius rn , we have

me v 2 1 Ze2

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= , (Centripetal force = Coulomb force), (3)
rn 4π0 rn2

where 0 is the permittivity of the space. Z = 1 corresponds to atomic H and

Z > 1 represent all hydrogenic ions, which can be treated in the same way as
H-atom within the Bohr’s model. Substituting for v from the orbital angular
momentum quantization condition

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nh
me vrn = , (4)
2π
we obtain

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n2 h2 0
rn = , n = 1, 2, 3, ... (5)
πme Ze2

Bohr radius rn ∝ n2 and inversely proportional to the nuclear charge +Ze.

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Eliminating rn , we obtain v = Ze2 /20 nh. Thus the total electronic energy E
reduces to
1 Ze2
 2
Ze2 Ze2

1 1 Ze
E = me v 2 − = − = − (6)
2 4π0 rn2 4π0 2rn rn 8π0 rn
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Substituting the value of rn from Eq. (5), we obtain

me e4 Z 2 2
13.6Z 2
 
−18 Z
E=− 2 2 = −2.1799 × 10 J = − eV. (7)
80 h n2 n2 n2
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In terms of the wave number, we find

me e4 Z 2
   2 2
Z 7Z
ν̄ = − 2 3 = −R H = −1.097 × 10 m−1 . (8)
n2 n2 n2
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80 ch
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The constant RH = 8m2ech e
3 is called the Rydberg’s constant. Thus for H-atom
0
(Z = 1), we recover the standard expression given in Eq. (2). An infinite series of
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lines (energy level diagram) are therefore expected, one for each n1 = 1 (Lyman),
2 (Balmer), 3 (Paschen), 4 (Bracket), 5 (Pfund) etc [Fig. 3]. In general, these
levels also have sublevels (further splitting) which for clarity are not shown in
the figure. Here, n = ∞ corresponds to ionization limit. A general expression
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for ionization potential is I.P.= 1.097 × 107 /n2 , where n is the orbital quantum
number from which the ionization takes place.

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Figure 3: Energy levels of H-atom (Adapted from PKG’s book).

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1.2 Further Modification:

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Although, Bohr’s model was quite successful in predicting the atomic spectrum
of H-atom under ordinary condition, it falls short to account for the fine split-
ting of the spectral lines observed when an excited atom is placed in an electric
(Stark effect) and magnetic (Zeeman effect) fields. With the concept of station-
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ary epileptic orbits in addition to Bohr’s circular orbits, Arnold Sommerfeld in

1915, proposed a set of semi-classical rules for quantization (Bohr-Sommerfeld
model of quantization) and provided a satisfactory explanation for the Stark
and Zeeman effects in the spectra of H and ionized He.

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 2 Inadequacy of Bohr’s Theory
• Bohr model tacitly assumed that classical mechanical laws of motion con-
tinue to hold even in atomic domain. This would mean that simultaneous

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measurements of position and momentum of the electron is possible with
arbitrary accuracy. This is against the fundamental percept of QM.
• While Bohr’s theory was quite successful in explaining the spectrum of H-
atom, the assumption behind the integral quantum number of the orbital
angular momentum, was remained illusive. Following some well known
facts from EM radiation, de Broglie proposed a new theory on dual nature
of matter to give a satisfactory answer to this underlying assumption.

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2.1 de Broglie’s Theory of Matter Wave
Luis de Broglie’s proposal in 1923 came out of following observations: The parti-

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cle character of light was a view that prevailed from early times and was upheld
by Issac Newton in 18-th century. Later, experimental observation of inter-
ference phenomena of light by Fresnel and others, led scientists to discard the
corpuscular theory of light and wave theory of light had been put forwarded.
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Other hand, experiments like Photo-electric effect and Compton effect could
only be explained by particle (photon) character of the light. This struck de
Broglie and led him to conclude that matter, apart from having particle char-
acter, may also have wavelike properties associated with it. The reason is the
only phenomena in physics in which the integers appear naturally are those of
interference and eigenvibrations and the explanations of which come through
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the consideration of light as wave. The presence of an integral quantum num-

bers in Bohr orbits was particularly intriguing in this context. He thought dual
nature of matter may then naturally led to appearance of integers in some of
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its behaviour and concluded further that wave and particle nature of matter
are not independent — rather they constitute two manifestations of reality and
there must exist a relationship between them. In order to derive the relation-
ship, de Broglie associated a periodic element with the corpuscular character of
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the material. However, the formal theory requires relativistic invariance w.r.t.
Lorentz transformation, a simple consideration of de Broglie matter wave circu-
lating endlessly in a Bohr orbit gives a qualitative explanation of the stationary
orbits. To amounts for a standing wave, the circumference 2πr of the orbit must
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be an integer multiple of the wavelength λ of the matter wave, i.e., 2πr = nλ.
This combined with Bohr quantum condition leads to:
nh h h
mvr = ⇒ 2πr = n =⇒ λ =
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2π mv mv
Thus the motion of a particle of mass m with velocity v, could be associated
with plane monochromatic wave of wavelength λ. More, generally, de Broglie
relationship λ = h/p, is of universal validity because of its relativistic invariance.
Manifestation of the matter or electron wave via diffraction effects with high
velocity electrons was first suggested by Frank Elsasser in 1925 such that de

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 Broglie wavelength associated with it are of the order of the inter-lattice dimen-
sions of the diffracting crystal. Started in 1922, first conclusive experimental
proof in support of de Broglie’s theory was provided by Clinton Davisson and
Lester Germer in 1928 in the form of a successful electron diffraction experiment

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on Ni crystal with accelerated electron beams of 50-600 V. Around the same
period, same effect also captured by George Thomson with 10,000-80,000 V
accelerated electrons in Al, Au, Pt thin films.

2.2 Problem of Simultaneous Measurements

Suppose, we have an ideal lens through which we can measure the y-component

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of the position of the particle, say an electron. Now, in order to observe the
particle, it is essential that at least one scattered photon must reach to our eye
after falling on the particle. So, the minimum uncertainty ∆y in measuring the
position will be given by

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λ
∆y = , (9)
sin α
where λ is wavelength of the light and α half angle subtended by the lens
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at the particle. According to de Broglie, photon also have a momentum h/λ
which could be any direction within an angular spread of α after the scattering.
Hence, the uncertainty in the y-component of the momentum of the photon is
≈ (h/λ) sin α. Since the momentum is conserved during collision (piph + piy =
pfph + pfy ), the uncertainty in y-component of the momentum of the particle will
be
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h
∆py ≈ sin α (10)
λ
This yields
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∆py ∆y ≈ h, (11)
which is independent of values of λ and α and can’t be avoided even in ideal
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situation. This is content of uncertainty principle formulated by Heisenberg in

1927 which is at the heart of QM and will be discussed further in later lectures.
However, the full consequence of de Broglie’s matter wave was worked out by
Erwin Schrödinger in 1926 and a new mechanics applicable to atomic systems
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was born with it — which we now call wave mechanics or quantum mechanics.

3 Schrödinger Wave Equation

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In all wave phenomena, some form of oscillations are involved and the amplitude
of oscillation (A) that undergoes periodic motion, is a solution of the wave
equation
∂2A ∂2A ∂2A 1 ∂2A
+ + = (12)
∂x2 ∂y 2 ∂z 2 v 2 ∂t2

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 with the wave velocity v. Schrödinger constructed a differential equation that
resembles Eq. (12) and called the amplitude function A as wave function Ψ —
known to be as Schrödinger equation (SE). A solution of the SE yields functional
dependence of Ψ from which all the properties of the system can be derived. A

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formal solution of the H-atom SE leads to quantum states of the Bohr model
as we will discuss later. Further, in terms of wave theory, when an electronic
transition takes place from higher energy to lower energy, it is not necessary
to invoke an electron jump. The frequency of radiation emitted is equal to
the difference in frequencies of the two standing waves and the increase of the
amplitude of one standing wave with the decrease in the other, leads to the
correct estimate of the intensities of the resulting spectral lines.

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The evolution of the SE from Eq. (12) can be traced as follows: For the wave
equation applied to matter wave, we can write
hν E
v = λν = = , (13)
mv p

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where p is the linear momentum. Following Eq. (12), if Ψ(x, y, z, t) is used to
represent the amplitude function of the matter wave, we can write
∂2Ψ ∂2Ψ ∂2Ψ 1 ∂2Ψ p2 ∂ 2 Ψ
∂x2
+
∂y 2
+
∂z 2
=
Gv 2 ∂t2
=
E 2 ∂t2
(14)

To ensure, standing wave solution, we write Ψ(x, y, z, t) = ψ(x, y, z)e−i2πνt ,

which upon substituting, yields
 2
∂ ψ ∂2ψ ∂2ψ 2
4π 2 p2 ψ −i2πνt

−i2πνt 2 2 p ψ −i2πνt
e + + = −4π ν e = − e (15)
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∂x2 ∂y 2 ∂z 2 E2 h2
Rearranging the above equation using the KE energy expression T = E − V =
p2 /2m, we obtain the standard form of the SE:
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h̄2
 2
∂2 ∂2
  
∂
− + 2 + 2 + V ψ(x, y, z) = Eψ(x, y, z). (16)
2m ∂x2 ∂y ∂z
Parallel to the development of wave mechanics, an alternative formulation of
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quantum mechanics (matrix mechanics) was developed by Max Born, Werner

Heisenberg and Max Jordon. In fact, the later appeared few months before the
publication of Schrödinger’s work. Despite their distinct mathematical frame-
works, both wave mechanics and matrix mechanics yield the same final results
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for any physical quantities at the end of the calculations. Finally, the equiva-
lence of the two mechanics was formally shown by Schrödinger and Carl Eckart
in 1926.
For discussing the electronic structure of atoms, we will use the SE as it
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is mathematically simpler to understand. Quantum mechanical results for an

atomic system are obtained by solving SE characteristic of the physical system
under consideration and a probabilistic interpretation of Ψ, due to Max Born is
utilized during the process. So, we will proceed with the postulates of QM.

1. Atomic Electronic Structure by P. K. Ghosh and P. K. Shukla. (PKG)