Introduction to Quantum

Chemistry
Dahlia C. Apodaca, PhD
Mapua Institute of Technology
2015
Historical Background of
Quantum Mechanics
• Late 19th century – investigations of electric discharge
tubes and natural radioactivity showed that atoms and
molecules are composed of charged particles
▫ Electrons – negatively charge particles
▫ Proton – positively charge; 1836x heavy as the e-
▫ Neutron – discovered in 1932; neutral and slightly heavier
than the proton

• 1909 – Rutherford, Geiger and Marsden carried out

experiments in which they passed a beam of alpha
particles through a thin metal foil and observed the
deflections of the particles by allowing them to fall on a
fluorescent screen.
• Rutherford observed that most of the alpha
particles passed through the foil undeflected,
few underwent large deflected, with some
deflected backwards.

• J. J. Thomson proposed in 1904 that the positive

charge were spread throughout the atom.

• Rutherford concluded that large deflections

could occur only if the positive charge were
concentrated in a tiny, heavy nucleus.
• In 1911, Rutherford proposed his “planetary”
model of the atom in which the electrons
revolved about the nucleus in various orbits.

• In 1913, Bohr applied the concept of

quantization of energy to the hydrogen atom.
▫ The electron is constrained to move only on one of
a number of allowed circles.
▫ When an electron makes a transition from one
orbit to another, a quantum of light of frequency is
absorbed or emitted;  = ΔE/h
▫ Could not account for chemical bonds in
molecules;
▫ Did not fit the helium spectrum
• Energy quantization was first introduced into
physics in 1900 by Planck.

• Planck derived the observed intensity distribution of

light emitted by a hot solid, energy in integral
multiples of h.

• In 1905, Einstein pointed out the dependence of the

kinetic energy of the electrons emitted in the
photoelectric effect on the frequency of the light
shining on the emitting metal
▫ Particle-like entities (photons) with each photon
having an energy, h
▫ Dual properties of light: wave- (evidenced by
diffraction) and particle- like
• Photons always travel at a speed c and have a
zero rest mass; must be treated relativistically

• Electrons always have  < c and a nonzero rest

mass; its speed is not too high can be treated
nonrelativistically.

• Uncertainty principle discovered in 1927 by

Heisenberg
▫ The more precisely we determine the position, the
less accurate is our determination of momentum
▫ Δx Δpx ≈ h
Photoelectric effect
• No electrons are ejected, regardless of the
intensity of the radiation, unless its frequency
exceeds a threshold value characteristic of the
metal.
• The kinetic energy of the ejected electrons varies
linearly with the frequency of the incident
radiation but is independent of its intensity.
• Even at low light intensities, electrons are
ejected immediately if the frequency is above
threshold.
• ½ me2 = h -  (work function)
• De Broglie suggested in 1923 that the motion of
electrons have a wave aspect
▫ An electron of mass m and speed  would have a 
associated with it such that,  = h / m = h/p
where p is the linear momentum
• In 1927, Davisson and Germer experimentally
confirmed de Broglie’s hypothesis by observing
diffraction effects by reflecting electrons from
metals
• In 1932, Stern observed the same effects with
helium atoms and hydrogen molecules.
• De Broglie relation:  = h/p
Time-dependent Schroedinger Equation
• Classical mechanics is applicable only to
macroscopic particles

• The motion of the particle is governed by Newton’s

second law
▫ F = m d2x/dt2

• “state” – a specification of the position and velocity

of each particle of the system at some instant of
time, plus specification of the forces acting on the
particles
• Quantum mechanics or wave mechanics – for
microscopic particles
▫ To postulate the basic principles and then use
these postulates to deduce experimentally testable
consequences such as the energy levels of atoms

• “state” – postulate the existence of a function of

the coordinates called the wave function or state
function, 

• The state in general, will change with time,  is a

function of time also
• One particle, one dimensional system
▫  =  (x, t)
• - ħ/i ( (x,t)/t) = - ħ/2m (2 (x,t)/x2 ) +
V(x,t) (x, t)
▫ Where ħ = h/2
• The concept of wave function and the equation
governing its change with time were discovered in
1926 by the Austrian physicist Schroedinger .
• Time-dependent Schroedinger equation
• i = -1
• m = mass of the particle
• V(x,t) = the potential energy function of the system
• From classical mechanics
▫ F(x,t) – force acting on the particle
▫ V is defined by, V(x,t)/x = - F(x,t)
• Time dependent Schroedinger equation
▫ Contains the 1st derivative of the wave function
with respect to time
▫ Allows the calculation of the future wave function
at any time
• WHAT INFORMATION DOES  GIVES ABOUT
THE RESULT OF A MEASUREMENT OF THE x
COORDINATE OF THE PARTICLE?
• Born postulated that
▫  (x, t)2 dx
 Gives the probability at time t of finding the particle in
the region of the x axis lying between x and x + dx.
 the bars denote the absolute value
 dx is an infinitesimal length on the x axis
▫  (x, t)2 - probability density for finding the particle
at various places on the x axis

• Quantum mechanics is basically statistical in nature;

can only predict the probabilities of various possible
results
• Quantum mechanics suggests the probability
patterns (wave functions) used to describe the
electron’s motion that behave like waves and satisfy
a wave equation
Time-Independent Schroedinger Equation

• Potential energy V is not a function of time but

depends only on x
• - ħ/i ( (x,t)/t) = - ħ/2m (2 (x,t)/x2 ) + V(x,t)
(x, t)
• Look for solutions that can be written as the product
of a function of time and a function of x
▫ (x,t) = f(t) (x)
▫ Time dependent wave function - 
▫  - for the factor which depends only on the coordinate
x
• Take partial derivatives:
▫ (x,t) /t = df(t)/dt (x) ,
▫ 2(x,t) / x2 = f(t)d2 (x) /dx2

▫ - ħ/i df(t)/dt (x) = - ħ2/2m f(t) d2(x) /dx2 + V(x) (x) f(t)
▫ - ħ/i 1/f(t) df(t)/dt = - ħ2/2m 1/ (x) d2(x) /dx2 + V(x)
• The function is independent of both variables, x
and t, it must be a constant, E.
▫ df(t) / f(t) = - iE/ħ dt
• Integrate both sides of this equation with respect
to t,
▫ ln f(t) = - iEt/ ħ + C
▫ where C is an arbitrary constant of integration
• f(t) = eC e-iEt/ħ = Ae -iEt/ħ
• f(t) = e -iEt/ħ
• - ħ/2m d2(x) /dx2 + V(x) (x) = E (x)
• d2(x) /dx2 + 82m/h2 [E – V(x)] (x) = 0
▫ Time-independent Schroedinger equation for a
single particle of mass m moving in one dimension
• E has the dimensions of energy; the energy of
the system
• Probability density,  (x, t)2
•   2 = *
•  (x, t)2 = (x)2
• The Schroedinger equation contains two
unknowns, the allowed energies E and the
allowed wave functions
• To solve for two unknowns, additional
conditions (called boundary conditions); the
boundary conditions determine the allowed
energies
• Only certain values of E allow  to meet the
boundary conditions
• In quantum mechanics, we must deal with
probabilities involving a continuous variable, the
x coordinate.
• Probability of finding the particle in a small interval
of the x axis lying between x and x + dx, dx being an
infinitesimal element of length.

• Probability is proportional to the length of the small

interval, dx and varies for different regions of the x
axis.

• The probability that the particle will be found

between x and x + dx is equal to g(x) dx, where g(x)
is some function which tells how the probability
varies over the x axis.

• The function g(x) is termed as the probability

density since it is a probability per unit length
• Probabilities are real, nonnegative numbers, g(x)
must be a real function that is everywhere
nonnegative

•  can take on negative and complex values and is

not a probability density

• Quantum mechanics postulates that the probability

density is given by 2
• What is the probability that the particle lies in some
finite region of space a  x  b?
▫ Sum up the probabilities of finding the particle in all
the infinitesimal regions lying between a and b
▫ A probability of 1 represents certainty
▫ When satisfies, it is said to be normalized
• Neglecting E in comparison with α
▫ d2 /dx2 = α,  = 1/α d2/dx2

• Conclude that  is zero outside the box:

▫ I = 0 III = 0

• For region II, x between zero and l, the potential

energy V is zero, and the Schroedinger equation
becomes
▫ d2II/dx2 + 2m/ħ2 EII = 0
▫ Where m = mass of the particle; E = its total
energy
▫ Linear homogeneous 2nd order differential
equation with constant coefficients
Particle in a One-Dimensional Box
• A particle subjected to a potential energy
function that is infinite everywhere along the x-
axis except for a line segment of length, l, where
the potential energy is zero.
to α to α

V(x)

I II III

x=0 x=l x
Potential energy for the particle in a one-dimensional box
• The auxiliary equation gives
▫ s2 + 2mEħ-2 = 0
▫ s =  (-2mE)1/2 ħ-1
• The energy E is equal to the potential energy, which is
zero, plus the kinetic energy, which is positive, so E is
positive and
▫ s =  (2mE)1/2 / ħ

• Linear homogeneous 2nd order differential

equation with constant coefficients:
▫ y” + py’ + qy = 0 (1) where p and q are
constants.
▫ To solve, assume a solution of the form y = esx
▫ The exponential function repeats itself when
differentiated,
▫ s2esx + psesx + qesx = 0
▫ s2 + ps + q = 0
▫ Auxiliary equation – a quadratic equation with two
roots s1 and s2 which, provided s1 and s2 are not
equal, give two independent solutions to (1)
• II = c1 e i(2mE)1/2 x/ ħ + c2 e -i(2mE)1/2 x/ ħ

• Let,
▫  = (2mE)1/2 x /ħ
▫ II = c1 ei + c2 e - i
▫ II = c1 cos  + ic1 sin  + c2 cos  - ic2 sin 
= (c1 + c2) cos  + (ic1 - ic2) sin 
= A cos  + B sin  where A and B are new arbitrary
constants.
• II = A cos[(2mE)1/2 x /ħ + B sin [(2mE)1/2 x /ħ]
• Determine A and B by applying boundary
conditions
• Wave function will be continuous
▫ If  is to be continuous at the point x = 0, then I
and II must approach the same value at x = 0
▫ lim I = lim II
▫ 0 = lim {A cos [(2mE)1/2 x /ħ + B sin [(2mE)1/2 x
/ħ]}
▫ A=0
• II = B sin [(2/h) (2mE)1/2 x]
• Applying the continuity condition at x = l
▫ B sin [(2/h) (2mE)1/2 l]
▫ B cannot be zero – empty box
• sin [(2/h) (2mE)1/2 l] = 0
• Zeros of the sine function occur at 0, , 2,
3,…
• (2/h) (2mE)1/2 l = n
• (42/h2) (2mE) l2 = n22
• E = n2 h2 / 8m l2
▫ Values of the energy are quantized
▫ Minimum value, greater than zero, for the energy
of the particle
• The constant B is still arbitrary – normalize
▫ II = B sin (nx/l)
▫ ʃ 2 dx = ʃ 2 dx
▫ ʃ I2 dx + ʃ II2 dx + ʃ III2 dx = 1
(-α to 0) (0 to l) (l to α)

• B2 ʃ sin2 (nx/l) dx = 1 = B2 l/2

▫ 2 sin2t = 1 - cos2 t
• B = (2/l)1/2
• II = (2/l)1/2 sin (nx/l)
 n=2 n=3
 
n=1 

x x x

Graphs of  for the three lowest energy particle in a box states.

Dynamics of Microscopic systems
▫ A wavefunction is just a mathematical function, which
may be large in one region, small in others and zero
elsewhere
▫ A wavefunction contains all the information it is
possible to know about the location and motion of the
particle it describes.
▫ If a wavefunction is large at a particular point, then the
particle has a high probability of being at that point; if
the wavefunction is zero at a point, then the particle
will not be found there.
▫ The more rapidly a wavefunction changes from place
to place, the higher the kinetic energy of the particle it
describes.
 

α
α

 
Problems
• Calculate the number of photons emitted by a 100-W yellow lamp in
1.0 s. Take the wavelength of yellow light as 560 nm and assume
100% efficiency.

• The speed of a 1.0-kg projectile is known to within 1 x 10-6 m/s.

Calculate the minimum uncertainty in its position.

• The work function for metallic cesium is 2.14 eV. Calculate the
kinetic energy and the speed of the electrons ejected by light of
wavelength 700 nm.

• Calculate the de Broglie wavelength of a mass of 1.0g travelling at

1.0 cm/s.

• An electron is confined to a molecule of length 1.0nm. What is a) its

minimum energy and b) the minimum excitation energy from that
state?

• What is the probability of locating the electron between x = 0 and x

= 0.2nm in its lowest energy state in the previous problem?
Degeneracy
• Stationary state – specified by giving the wave
function 
• Energy level – specified by giving the value of
the energy
• An energy level that corresponds to more than
one state is said to be degenerate
• Degree of degeneracy - the number of different
states belonging to the level
Operators
• Operator – a rule for transforming a given function
into another function.
▫ e.g. d/dx
▫ (d/dx) f(x) = f’(x)
• Let  – an arbitrary operator
• If  transforms f(x) into the function of g(x)
▫ Âf(x) = g(x)
• If  is the operator d/dx, g(x) = f’(x)
• If  is the operator “multiplication by 3x2,” g(x) =
3x2f(x)
• If  = log, g(x) = log f(x)
• The sum of two operators  and B is defined by
▫ (Â + B) f(x) = Âf(x) + Bf(x)
▫ (ln + d/dx) f(x) = ln f(x) + (d/dx) f(x)
= ln f(x) + f’(x)
▫ (Â - B) f(x) = Âf(x) - Bf(x)

• The square of an operator is defined by

▫ Â2f(x) = Â [Âf(x)]
▫ Ex. (d/dx)2 f(x) = (d/dx) [(d/dx) f(x)]
= (d/dx) [f’(x)] = f”(x)
= (d2/dx2) f(x)
▫ Therefore (d/dx)2 = d2/dx2
• The product of two operators is defined by
▫ (Â B)f(x) = Â[ Bf(x) ]
▫ Apply the operator B to the function f(x) to get a
new function
▫ Then apply the operator  to the new function
• Two operators are equal if they produce the
same result when operating on an arbitrary
function
▫ B = C if and only if Bf = Cf for every function f.
• The operator ÂB – B – commutator of  and B
and is symbolized by [Â,B]
 Operators in Quantum Mechanics
• Each physical property of a system has a
corresponding operator
▫ Ex. ṕx = ħ/ i /x
• Hamiltonian, H – the expression for the energy as a
function of coordinates and momenta
▫ E = 1/2m (Px2 + Py2 + Pz2) + V(x, y, z, t) = H
• Hamiltonian operator, for a one particle system
▫ Ȇ = Ĥ = -ħ2/2m (2/x2 + 2/y2 + 2/z2) + V(x, y, z,
t)
▫ Ĥ = - (ħ2/2m) 2 + V
• Time-dependent Schrodinger equation
▫ - ħ/i /t = Ĥ

• Time independent Schrodinger equation

▫ Ĥ = Ȇ

• Eigenfunction – when an operator  applied to

the function f gives the function back again but
multiplied by the constant c, that is, when
Âf = cf
• f is an eigenfunction of  with eigenvalue of c
•  is an eigenfunction of the Hamiltonian
operator Ĥ, the eigenvalue is the allowed energy
E

• Seatwork
▫ Which of the functions are eigenfunctions of
d2/dx2?
 Sin 3x
 6 cos 4x
 5x3
 1/x
 3e-5x
 ln 2x
▫ For each eigenfunction, state the eigenvalue?
Problem
• For a particle in a one-dimensional box
stationary state, show that
▫ <px> = 0
▫ <x> = a/2
▫ <x2> = a2(1/3 - ½ n22)
1-D Harmonic Oscillator
• Useful model for treating the vibration of a
diatomic molecule
• Relevant to vibrations of polyatomic molecules