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26491797 457454 Physical Chemistry Quantum Chemistry[1]|Views: 153|Likes: 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* = 4*π *0*N*2

~2

*Zmee*2

(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/*2*π* is Planck’s constant

divided by 2*π.
*

The constant quantity 4*π *0~2

*mee*2 appears often and is given the special symbol* a*0 ≡

4*π *0~2

*mee*2 = 0*.*52918 Å and is called the Bohr radius.

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

*EN* =−*Z*2

*µ e*2

2*a*0

*¶* 1

*N*2*.
*

(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* =∞

*E*ionize =* E*∞−*E*1 = −*Z*2

*e*2

2*a*0

*µ* 1

∞2 − 1

12

*¶* =* e*2

2*a*0

(1.3)

19

—* E*ionize =* e*2

2*a*0 = 13*.*606 eV= 109,667 cm−1

=*R*.* R*is called the Rydberg

constant.

—* E*ionize 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

*Ej*−*Ek* =* e*2

2*a*0

*µ* 1

*N*2

*j* − 1

*N*2

*k
*

*¶* =* Rµ* 1

*N*2

*j* − 1

*N*2

*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,* ψ*∗*ψ* =* |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*|ψ*(*x,y,z*)*|*2

*dxdydz
*

(or* |ψ*(*r,θ,φ*)*|*2

*r*2

sin*θdrdθdφ* in spherical coordinates).

22

22

Properties of the wavefunction

*•* Single valueness

*•* continuous and ﬁnite

*•* continuous and ﬁnite ﬁrst derivative

*• R*space*|ψ*(*x,y,z*)*|*2

*dxdydz <*∞

Normalization of the wavefunction

In order for* |ψ*(*x,y,z*)*|*2

to be exactly interpreted as a probability dis-

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

That is,* ψ*unnorm =* Nψ*norm, where*N* =* qR*space*|ψ*unnorm(*x,y,z*)*|*2

*dxdydz
*

This assures that* R*space*|ψ*norm*|*2

*dxdydz* = 1 as expected for a proba-

bility distribution

From now on we will always normalize our wavefunctions.

Significance Levels-0.05, 0.01?????

English Through Tamil

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Ani So Tropic Diffusion in Image Processing

34185221 the Foundations of Math[1]

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