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26491797 457454 Physical Chemistry Quantum Chemistry[1]

26491797 457454 Physical Chemistry Quantum Chemistry[1]

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1.2.1. First Attempts at the Structure of the Atom

The “solar system” model.

The electron orbits the nucleus with the attractive coulomb force balanced
by the repulsive centrifugal force.

Flaws of the solar system model

Newton: OK√
Maxwell: problem√

17

— As the electron orbits the nucleus, the atom acts as an oscillating dipole

— The classical theory of electromagnetism states that oscillating dipoles
emit radiation and thereby lose energy.

— The system is not stable and the electron spirals into the nucleus. The
atom collapses!

Bohr’s model: Niels Bohr (1885—1962)

18

Atoms don’t collapse =⇒ what are the consequences

Experimental clues

Atomic gases have discrete spectral lines.
If the orbital radius was continuous the gas would have a continuous spec-

trum.

Therefore atomic orbitals must be quantized.

r = 4π 0N2

~2

Zmee2

(1.1)

where Z is the atomic number, me and e are the mass and charge of the
electron respectively and 0 is the permittivity of free space. N is a positive
real integer called the quantum number. ~ = h/2π is Planck’s constant
divided by 2π.

The constant quantity 4π 0~2

mee2 appears often and is given the special symbol a0 ≡

4π 0~2
mee2 = 0.52918 Å and is called the Bohr radius.

The total energy of the Bohr atom is related to its quantum number

EN =−Z2

µ e2
2a0

1

N2.

(1.2)

Tests of the Bohr atom

Ionization energy of Hydrogen atoms
— The Ionization energy for Hydrogen atoms (Z = 1) is the minium
energy required to completely remove an electron form it ground state,
i.e., N = 1→N =∞

Eionize = E∞−E1 = −Z2

e2

2a0

µ 1

∞2 − 1
12

= e2
2a0

(1.3)

19

Eionize = e2

2a0 = 13.606 eV= 109,667 cm−1

=R. Ris called the Rydberg

constant.

Eionize experimentally observed from spectroscopy is 13.605 eV (very
good agreement)

Spectroscopic lines fromHydrogenrepresent the difference inenergy between
the quantum states

— Bohr theory: Difference energies

EjEk = e2
2a0

µ 1

N2

j − 1

N2

k

= 1

N2

j − 1

N2

k

(1.4)

Initial state Nk Final States Nj Series Name
1

2,3,4,···

Lyman

2

3,4,5,···

Balmer

3

4,5,6,···

Pachen

4

5,6,7,···

Brackett

5

6,7,8,···

Pfund

— Since the orbitals are quantized, the atom may only change its orbital
radius by discrete amounts.

— Doing this results in the emission or absorption of a photon with energy

˜v = 4E
hc

(1.5)

Failure of the Bohr model

No fine structure predicted (electron-electron coupling)
No hyperfine structure predicted (electron-nucleus coupling)
No Zeeman effect predicted (response of spectrum to magnetic field)

20

Spin is not included in theory

The Bohr quantization idea points to a wavelike behavior for the electron.

The wave must satisfy periodic boundary conditions much like a vibrating ring

∗∗∗ See Fig. 11.9 Laidler&Meiser∗∗∗

The must be continuous and single valued

Particles have wave-like characteristics

The Bohr atom was an important step towards the formulation of quantum theory

Erwin Schrödinger (1887—1961): Wave mechanics
Werner Heisenberg (1902—1976): Matrix mechanics
Paul Dirac (1902—1984): Abstract vector space approach

21

2. The Postulates of Quantum
Mechanics

2.1. Postulate I

Postulate I: The state of a system is defined by a wavefunction, ψ, which con-
tains all the information that can be known about the system.

We will normally take ψ to be a complex valued function of time and coordi-
nates: ψ(t,x,y,z) and, in fact, we will most often deal with time independent
“stationary” states ψ(x,y,z)

Note: In general the wavefunction need not be expressed as a function of coordi-
nate. It may, for example, be a function of momentum.

The wavefunction ψ represents a probability amplitude and is not directly observ-
able.

However the mod-square of the wavefunction, ψψ = |ψ|2

, represents a probability

distribution which is directly observable.

That is, the probability of finding a particle which is described by ψ(x,y,z) at the
position between x and x+dx, y and y+dy and z and z+dz is(x,y,z)|2

dxdydz

(or(r,θ,φ)|2

r2

sinθdrdθdφ in spherical coordinates).

22

22

Properties of the wavefunction

Single valueness
continuous and finite
continuous and finite first derivative
• Rspace(x,y,z)|2

dxdydz <

Normalization of the wavefunction

In order for(x,y,z)|2

to be exactly interpreted as a probability dis-

tribution, ψ(x,y,z) must be normalizable.

That is, ψunnorm =norm, whereN = qRspaceunnorm(x,y,z)|2

dxdydz

This assures that Rspacenorm|2

dxdydz = 1 as expected for a proba-

bility distribution

From now on we will always normalize our wavefunctions.

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