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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
▫ - 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 + 82m/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.
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
• 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
• (42/h2) (2mE) l2 = n22
• 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 (nx/l)
▫ ʃ 2 dx = ʃ 2 dx
▫ ʃ I2 dx + ʃ II2 dx + ʃ III2 dx = 1
(-α to 0) (0 to l) (l to α)
x x x
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 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.
• 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 n22)
1-D Harmonic Oscillator
• Useful model for treating the vibration of a
diatomic molecule
• Relevant to vibrations of polyatomic molecules