CHEM 452 Physical Chemistry (Quantum Chemistry)

Quantum chemistry is “Quantum Mechanics” applied to chemistry

Quantum mechanics is a math/mechanics framework for the physics of a tiny particle

• Classical Mechanics (Review)

ü A particle trajectory is given as a series of the precise positions at a series of fixed time points
ü Two characteristics of classical mechanics (distinct from those of quantum mechanics)
1. With a given pair of position and momentum of a particle at a fixed time point t, its precise
trajectory after t is known.
2. A particle can take any arbitrary values for its potential and kinetic energy.
ü Commonly used quantities/variables/parameters
→
o Position: in 3D, r , (x, y, z) for Cartesian coordinates or (r, θ, 𝜙) for spherical polar coordinates
; in 1D, typically, use x for Cartesian and r for polar coordinate

Integration of a function over the entire space:

∞ ∞ ∞ 2π π ∞
∫ ∫ ∫ f (x, y, z)dx dy dz ∫ ∫ ∫ f (r, θ , φ )r 2 dr sin θ dθ dφ
−∞ −∞ −∞ 0 0 0

! !
! dr ! dφ
o Velocity: v = (angular: ω = ) ; v = dx/dt in 1D
dt dt
! ! ! !
o Momentum: p = mv (angular: J = Iω , where I is the moment of inertia)
o Kinetic energy : Energy associated with particle motion
p 2 mv 2
§ Translational energy: E = K = T = Ek = =
2m 2
J 2 Iω 2
§ Rotational energy: E = =
2I 2
!
o Potential energy : Energy deposited in a particle to be at a specific point in space, V (r )

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ü Law of energy conservation (Newton’s 1st law)
E = K + V = constant
ü Force, momentum, acceleration (Newton’s 2nd law)
! !
dp dv
F= =m
dt dt
ü Potential energy and force
dV
F =− !
dr
; Particles move toward –dV/dr gradient and end up at a minimum V point where dV/dr = 0.

Ex) How classical mechanics “describes” a particle motion (position and momentum/energy):
1 dimensional (1D) vibrational motion (a particle on a spring)

As momentum is related to force that is given by the spring,

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 dp dv d 2x
⇒ F = −kx = =m =m 2
dt dt dt
2
d x
⇒ −kx = m 2 ! (i)
dt
x : function of t
2nd derivative of a function = − function
⇒ x(t) = Acos(ω t) + A'sin(ω t)

To determine the unknowns,

dx
⇒ = −Aω sin(ω t) + A'ω cos(ω t)
dt
d 2x
⇒ 2 = −Aω 2 cos(ω t) − A'ω 2 sin(ω t) = −ω 2 (Acos(ω t) + A'sin(ω t)) = −ω 2 x
dt
d 2x
⇒ 2 = −ω 2 x ! (ii)
dt
compare (i) and (ii)
k k
⇒ ω2 = ⇒ω =
m m
at t = 0 (right before letting go), x = xi
⇒ xi = Acos(ω ⋅ 0) + A'sin(ω ⋅ 0) = A
at t = 0 x should be at its max
dx
⇒ = −Aω sin(ω t) + A'ω cos(ω t) = 0 @ t = 0
dt
⇒ A' = 0
k
⇒ x(t) = xi cos( t)
m

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 Then it follows that the momentum is,
dx
p(t) = mv = m = m ⋅ −xiω sin(ω t)
dt

And the kinetic energy is,

2 2 2 2 2
p 2 (−mxiω sin(ω t)) m xi ω sin (ω t) 1 2 2 2 k
K (t) = = = = mxi ω sin (ω t) ;ω 2 =
2m 2m 2m 2 m
1
= kxi2 sin 2 (ω t)
2

The total energy is fixed and determined by how much the spring was stretched initially.
dV dV
For Vi (V @ t=0), F = −kx = − ! = −
dr dx
dV
⇒ kx =
dx
⇒ dV = kxdx
Vi xi
⇒ ∫ 0
dV = ∫ 0
kx dx
1
⇒ Vi = kxi2 = total E of the oscillating mass
2
1
Total E = kxi2 = K (t) +V (t)
2
1 1 1 1
⇒ V (t) = E − K (t) = kxi2 − kxi2 sin 2 (ω t) = kxi2 (1− sin 2 (ω t)) = kxi2 cos 2 (ω t)
2 2 2 2

Grand Conclusion
Classical mechanics can mathematically “model” the precise trajectory (position and momentum) of a
particle based on a given set of initial conditions. People found that this framework no longer works
for particles that are extremely small (e.g., electrons, atoms, and molecules). They needed a new
framework to describe the behavior of such small particles and came up with one about a century ago.
This new mathematical framework is named quantum mechanics. Quantum mechanics is based on an
assumption that a particle has quantized energy and can absorb or emit only an integer multiple of a
minimum quantized energy, or an energy quantum.

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1. Historical background of quantum mechanics
Observations that could not be explained with classical mechanics
1.1. Quantization of energy
(a) Black body radiation
• In classical electrodynamics, charged particle oscillation results in electromagnetic wave radiation.
Charged particles can also absorb light (oscillating electromagnetic field) to be excited and resonate
with the electric field (e-field) of light.

ü Characteristics of oscillators
1. They have a (fixed) unique oscillation frequency
2. They can be heated (excited) to have any arbitrary amount of energy

• A black body contains oscillators that collectively cover the entire frequency range of electromagnetic
radiation. Therefore, it absorbs all colors of light, hence looks black. When heated to any arbitrary
temperature, it should emit all colors of light including UV, x-ray, γ-ray, etc, which is not true. This is
called “UV catastrophe”.

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• Max Planck, without any physical basis, derived a formula that can fit the observed black-body
radiation (the dotted line in the chart above) by introducing a minimum “quantized” energy, or an
energy quantum, ΔE , to excite an oscillator. He assumed that the energy quantum ΔE is linearly
proportional to the oscillation frequency ν. The linearity constant is called “Planck’s constant” which
when multiplied to the frequency of an oscillator sets its minimum energy quantum.
hc
ΔEoscillator = hν oscillator =
λoscillator
8π hc $ 8π hc '
⇒ρ= 5 hc/ λ kBT &= 5 ΔE/kBT )
λ (e −1) % λ (e −1) (

for a long λ (small ΔE),

e hc/λkT −1 ≈ 1+ hc / λ kBT −1 = hc / λ kBT
8π hc 8π kBT
⇒ρ= 5 = ; Rayleigh − Jeans Law
λ hc / λ kBT λ4

for a short λ (big ΔE),

e hc/λkT = e ΔE/kBT >> 1
8π hc 8π kT −hc/λkBT
⇒ ρ = 5 hc/λkBT = e
λe λ5
⟹ The exponential term e-hc/λkT becomes really small
⟹ no significant radiation at short wavelengths

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è If the minimum energy quantum required to excite an oscillator is larger than the thermal energy
available at T, the oscillator cannot be excited at T. Ex) UV oscillators have a much higher minimum
“energy quantum” than kBT @ 1000K è Heating something @ 1000K cannot result in UV emission.

(b) Heat capacity

" ∂U %
CV = $ '
# ∂T &V
U = 3N A kBT = 3RT; 3kBT per oscillator (atoms in a 3D lattice)
⇒ CV = 3R
However, @ low T, CV is much smaller than 3R.
Einstein, by applying the concept of excitation energy quantization for thermal oscillators, derived a
formula that can explain CV curve @ low T.

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(c) Line spectra of atoms and molecules
Atoms and molecules when heated emit radiations at discrete wavelengths.
è Atoms and molecules occupy discrete energy states.
Spectral transition ΔE = hν ; energy is quantized (= ℏω in angular frequency, ω = 2πν)

è Bohr model ; discrete e- (electron) orbits

1.2. Wave-particle duality

• Electron diffraction: electrons form a diffraction pattern when passing through a double slit è
electrons behave like a wave

• Photoelectric effect
e- ejected from a metal surface by light illumination (photoelectron)

No matter how intense the light is, no e- comes out if ν < νth.
è Einstein proposed that light is particle-like. Each particle (photon) conveys an energy quantum hν.
è No matter how many photons hit the metal surface, if ν < νth , no electron comes out.
Later by de Broglie, everything behaves like particle and wave at the same time.
è The physical properties of a particle can be described as those of a wave. e.g., p = h/λ

o Energy quantization: E = nhν , where n = 1, 2, 3, …

o Wave-particle duality: λ = h/p or p = h/λ ; de Broglie relation

⇨ The starting point of quantum mechanics: Why don’t we model the properties of a particle as
those of a wave whose energy is quantized?

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Ex1) What is the de Broglie wavelength of a 100g baseball flying at 132.6 km/s?
h h 6.63×10 −34 J ⋅ s
λ= = = = 0.500 ×10 −37 m ; negligibly small
p mv 0.100kg ⋅132.6 ×10 3 m / s

Ex2) What is the de Broglie wavelength of an electron traveling at 1.0 % of speed of light?
h h 6.63×10−34 J ⋅ s
λ= = = 8
= 2.4 ×10−12 m = 2.4 A! ; ~ size of an atom
p mv 9.11×10 kg ⋅ 0.010 ⋅ 3.0 ×10 m / s
−31

è This wavelength is on the atomic length scale.

o The classical wave equation (1D)

; describes t-dependent motion of a wave in 1 dimension, where u (x,t)= wave amplitude at x and t, x =
position, t = time, v = velocity, λ = wavelength, k = wave number (or spatial frequency 2π/λ = how many
unit wavelengths can fit in 2π), ω = angular frequency, v = linear frequency (*NOTE that greek “nu” v
looks the same as the italicized alphabet “v” v, but they denote two different things. I will try to be clear
whenever needed).

1 ∂2 u(x, t) ∂2 u(x, t)
=
v 2 ∂t 2 ∂x 2
2π p p v 2π
= 2π = ⇒ p = !k, ω = 2π =
⇒ u(x, t) = Aei(kx−ωt ) = Aeikx e−iωt ; k = v
λ h ! λ λ
2π
i ( x−vt ) ) # 2π & # 2π &,
⇒ u(x, t) = Ae λ = A *cos% (x − vt)( + isin % (x − vt)(-
+ $λ ' $λ '.
; wave with 2π/λ spatial frequency moving to à direction at speed v

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o Eigenvalue equations; A math framework for quantum mechanics
Eigenvalue/Eigenfunction(Eigenvector) can be applied to functions and function spaces (matrices)

When the result of an operator applied to a function is the same function multiplied by a constant, the
function is called an “eigenfunction” of the operator and the constant is called an “eigenvalue” of the
function for the operator.

d
Ex1) Is a function eiωt an eigenfunction of an operator dt ?

d
f = eiωt , Â =
dt
d iωt
⇒ Âf = e = iω eiωt = iω f = af
dt
è f is an eigenfunction of the operator d/dt and its eigenvalue is iω

d2
2
Ex2) Is a function cos(ωt) an eigenfunction of an operator dt ?

d2
f = cos(ω t) , Â =
dt 2
d2 d
⇒ Âf = 2 cos(ω t) = ω sin(ω t) = −ω 2 cos(ω t) = −ω 2 f = af
dt dt
è f is an eigenfunction of the operator d2/dt2 and its eigenvalue is –ω2

d
Ex3) Is a function cos(ωt) an eigenfunction of an operator dt ?

d
f = cos(ω t) , Â =
dt
d
⇒ Âf = cos(ω t) = ω sin(ω t) ≠ af
dt
è f is NOT an eigenfunction of the operator d/dt

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