Quantized Energies Explain Atomic and

Molecular Emission and Absorption Spectra

Emission spectrum of excited mercury:
Spectral lines (projections of slit)

Frequency (Energy) →

Mercury Lamp!

A molecule (ScF) shows a more complex

spectrum (absorption and emission)

Frequency (Energy) → Nils Walter: Chem 260

Wave-Particle Dualism: A Particle is Spread
Through Space Like a Wave
de Broglie relation:
h
λ=
p

Trajectory of a classical particle

Fuzziness
Paradigm shift
Heisenberg:
Ψ Ÿ Heisenberg’s Physics Nobel
uncertainty principle prize 1932

It is impossible to specify simultaneously,

with arbitrary precision, both the
momentum and Nils theWalter: Chem 260
position of a particle
Heisenberg’s Uncertainty Principle, less fuzzy
A classical particle A wave-like particle
A single wave (with
defined momentum) has
an ill-defined location

The superposition of
many waves (different
momenta) to
constructively interfere in
one position, but
destructively in all others,
yields a well-defined
location, but ill-defined
momentum

1 h 1
Quantitative (one dimension): ∆p∆x ≥ = 
2 2π 2
Constrained only along the
Nils sameChem
Walter: axis!
260
 Quantum Mechanics:
The Schrödinger Equation
Differential equation for a one-dimensional
wave with amplitude u(t,x) = Ψ(x)e2πiνt :
d 2u 1 d 2u d 2 Ψ 4π 2ν 2
Heisenberg: Schrödinger:
Physics Nobel Physics Nobel 2
= 2 2 Ÿ 2
+ 2
Ψ=0
prize 1932 prize 1933 dx v dt dx v
Matrix Wave time-independent wave function
mechanics mechanics
and 1 2 p2
Quantum mechanics
Etotal = Ekin + E pot = mv + V = +V
2 2m
mv = p
Ÿ p= 2m( E − V )
Ÿ −
 2
d 2
Ψ
h
and λ = =
h v + VΨ = EΨ
= 2m dx 2
p 2 m( E − V ) ν
de Broglie relation ∧
Nils Walter: Chem 260
Hamilton Operator H Ψ = EΨ
 The Postulates of Quantum Mechanics
1.) The physical state of a particle or system of particles can be
described by a wavefunction Ψ(x) or Ψ(x, y, z, t,...)

2.) This wavefunction is a solution to the Schrödinger equation

under the specific boundary conditions of the system:
∧ 2 d 2
∧ h
H Ψ = EΨ; with H = − +V and  =
2m dx 2
2π
“Energy Eigenvalue” of the system (discrete!)
3.) The average value (“expectation value”) of any physical
property can be calculated from:
+∞ ∧ +∞ ∧
< F >= ³ Ψ ( x) F Ψ ( x)dx e.g., < x >= ³ Ψ ( x) x Ψ ( x)dx
−∞ −∞
Nils Walter: Chem 260
The Born Interpretation of the Wavefunction
Statistical (or probabilistic) interpretation of Ψ:
“The probability of finding a particle in a small
(strictly, infinitesimal) region of space of volume
δV is proportional to Ψ2δV, where Ψ is the value
of the wavefunction in the region”

Ψ2 is a probability density Born:

Physics Nobel
prize 1954

Although Ψ does not have a direct

physical interpretation, its square tells
us the probability of finding it in a
certain region - in accordance with
Heisenberg’s uncertainty principle
Nils Walter: Chem 260