Fundamentos Basicos

Funccion de onda
Principio de incertidumbre de Heisenberg
Equacion de Schrodinger
Hamiltoniano (Operador de energia total)

3-dimensiones

Sistema de n particulas

Algebra de operadores
si

si

Operadores de diferentes variables

Operadores lineales

Operadores Hermitianos

Valores esperados

Principio de incertidumbre

Hamiltoniano de un sistema polielectronico en apromaxicion de Born

Y Openheimer

Aproximacion de Born y Openheimer

Particula en un pozo de Potencial

Particula en un pozo de Potencial (continuacion)

Particula en un pozo de Potencial (aplicacion)

cyanine
pinacyanol
dicarbocyanin
e

L (pm)
556
834
1112

Theory
328 nm
453 nm
580 nm

Experiment
523 nm
605 nm
706 nm

Principio de Pauli

Aproximacion de Hartree-Fock
Hamiltonian contains two terms that act
on one electron at a time the kinetic
energy and the electron-nucleus
attraction, and a term that describes the
pairwise repulsion of electrons. The latter
depends on the coordinates of two
electrons at the same time
To avoid this problem the
independent particle approximation is
introduced : the interaction of each
electron with all the others is treated
in an average way.
Then the Schrdinger equation which initially
depended on the coordinates x (representing
spatial and spin coordinates) of all electrons
can be reduced to a set of equations

Spin orbital

He atom

Koopmans' Theorem

The Pauli principle states that the wavefunction must change sign
when two independent electronic coordinates are interchanged

For two electron system

Slater determinant

Principio variacional

Teoria de perturbacion independiente de tiempo

Teoria de functionales de la densidad

Atomo de Hidrogeno y Atomos Polielectronicos

solucion

Simetria de los orbitales

???

The Aufbau Principal

When placing electrons into orbitals in the
construction of polyelectronic atoms, we use the
Aufbau Principle.

This principle states that in addition to adding

protons and neutrons to the nucleus, one simply
adds electrons to the hydrogen-like atomic orbitals
Pauli exclusion principle: No two electrons may
have the same quantum numbers. Therefore, only
two electrons can reside in an orbital
(differentiated by ms).

The Aufbau Principal (cont.)

Finally, orbitals are filled starting from the lowest
energy.
Example: Hydrogen
1s1
1s

2s

2p

Example: Helium (Z = 2)
1s2
1s

2s

2p

The Aufbau Principal (cont.)

Lithium (Z = 3)
1s22s1
1s

2s

Berillium (Z = 4)

2p
1s22s2

1s

2s

2p

Boron (Z = 5)
1s22s22p1
1s

2s

2p

The Aufbau Principal (cont.)

Carbon (Z = 6)
1s22s22p2
1s

2s

2p

HundsRule:Lowestenergyconfigurationis
theoneinwhichthemaximumnumberofunpairedelectrons
aredistributedamongstasetofdegenerateorbitals.

Nitrogen (Z = 7)
1s22s22p3
1s

2s

2p

The Aufbau Principal (cont.)

Oxygen (Z = 8)
1s22s22p4
1s

Fluorine (Z = 9)

2s

2p
1s22s22p5

1s

2s

2p

Neon (Z = 10)
1s22s22p6
1s

2s

2p

full

The Aufbau Principal (cont.)

Sodium (Z = 11)
Ne

1s22s22p63s1

[Ne]3s1

3s

Argon (Z = 18)
[Ne]3s23p6

Ne
3s

3p

The Aufbau Principal (cont.)

Wenowhavetheorbitalconfigurationsforthefirst18elements.

Elementsinsamecolumnhavethesame#ofvalenceelectrons!

The Aufbau Principal (cont.)

SimilartoSodium,webeginthenextrowoftheperiodic
tablebyaddingelectronstothe4sorbital.
Whynot3dbefore4s?
3disclosertothenucleus
4sallowsforcloser
approach;therefore,is
energeticallypreferred.

The Aufbau Principal (cont.)

ElementsZ=19andZ=20:
Z=19,Potassium:1s22s22p63s23p64s1=[Ar]4s1
Z=20,Calcuim:1s22s22p63s23p64s2=[Ar]4s2

ElementsZ=21toZ=30haveoccupieddorbitals:
Z=21,Scandium:1s22s22p63s23p64s23d1=[Ar]4s23d1
Z=24,Chromium:[Ar]4s13d5

exception

Z=30,Zinc:1s22s22p63s23p64s23d10=[Ar]4s23d10

The Aufbau Principal (cont.)

Thisorbitalfillingschemegivesrisetothemodern
periodictable.

The Aufbau Principal (cont.)

AfterLanthanum([Xe]6s25d1),westartfilling4f.

The Aufbau Principal (cont.)

AfterActinium([Rn]7s26d1),westartfilling5f.

The Aufbau Principal (cont.)

Headingoncolumngiventotalnumberofvalence
electrons.

The Aufbau Principal (cont.)

Radio atomico

Potencial de ionizacion

X(g) = X(g)+ + e-

H = IP

Afinidad Electronica
X(g) + e- = X(g)-

H = EA

Electronegativit
y
Mulliken IP+AE/2

Pauling

Mulliken vs Pauling

Electronegatividad (cont)
Atomos pequeos
Son electronegativos

Orbitales Hibridos

Etileno

Acetileno

Elementos de teoria de grupos de simetria

Elementos de simetria molecular

Character table for D3h point group

2C3

3C'2

2S3

3v

linear,
quadratic
rotations

A'1

A'2

-1

-1

Rz

E'

-1

-1

(x, y)

A''1

-1

-1

-1

A''2

-1

-1

-1

E''

-1

-2

(Rx, Ry)

x2+y2, z2

(x2-y2, xy)

(xz,yz)

Character table for Td point

group
8C3

3C2

6S4

6d

A1

A2

-1

-1

linear,
rotations

quadratic
x2+y2+z2

(2z2-x2-y2,
x2-y2)

-1

T1

-1

-1

(Rx, Ry, Rz)

T2

-1

-1

(x, y, z)

(xy, xz, yz)

Teoria de orbitales moleculares

Teoria de orbitales moleculares

Hermitian Operator

Teoria de orbitales moleculares (cont)

S=0

Teoria de Huckel

HOMO

LUMO

FUERZAS INTERMOLECULARES

FUERSAS INTERMOLECULARES
Melting Points and Boiling Points of Similar Substances with Increasing Formula Weights
Substance

F2
Cl2
Br2
I2

FW (g/mol)
38
71
160
254

mp (C)
-220
-100.98
-7.2
113.5

bp (C)
-188
-34.6
58.78
184.35

Melting Points and Boiling Points of Substances with Similar Formula Weights
Substance

FW (g/mol)

mp (C)

bp (C)

F2

38

-220

-188

NO

30

-164

-152

CH3OH

32

-94

65

Ca

40

893

1484

NaF

42

993

1695

dispersion

FUERZAS INTERMOLECULARES
Dipolo-dipolo

Ion-dipolo

u-momento dipolar
Q-carga de ion
Puentes de hidrogeno

Dipolo-dipolo
inducido

FUERSAS INTERMOLECULARES

problemas

Calculate the wavelength and frequency of the photon emitted if an

electron in a onedimensional
box of length 1.00 nm (1.00109 m) makes a transition from n 3 to
n 2
and the energy difference is entirely converted into the energy of the
photon
Pretend that electrons are bosons with zero spin. Describe
how the ground state of the helium atom would differ from
the actual ground state in the orbital approximation.

sp Hybrid Orbitals
F

Be

Be*

BF3

sp2 and sp3 Hybrid Orbitals

CH4

H2O

PF5

Valence Shell Electron Pair Repulsion (VSEPR) Model

The bond angles decrease as

the number of nonbonding
electron pairs increases

Electrons in multiple bonds, like nonbonding electrons, exert a greater

repulsive force on adjacent electron pairs than do single bonds

Geometries of
Molecules with
Expanded Valence
Shells

If there is a non-bonding pair of electrons (a "larger" electron cloud),

it will go in the axial position to minimize electron repulsion

Teoria de Enlaces de Valencia

H2

MO de H2

Teoria de Resonancia
Manysimpleorganiccompounds,suchasmethane,ethene,
etc.,canbeadequatelyrepresentedbyasingleLewis
structure:
methane - CH4
ethene - H2C=CH2

Teoria de Resonancia

Acidos y Bases

Brnsted Acid-Base Theory

Brnsted argued that all acid-base reactions involve the transfer of an H+ ion, or proton. Water reacts
with itself, for example, by transferring an H+ ion from one molecule to another to form an H3O+ ion
and an OH- ion.

Acid-Dissociation Equilibrium Constant

Acids are often divided into categories such as "strong" and "weak." One measure of the strength of an
acid is the acid-dissociation equilibrium constant, Ka, for that acid.
When Ka is relatively large, we have a strong acid.

HCl: Ka = 1 x 103
When it is small, we have a weak acid.

CH3CO2H: Ka = 1.8 x 10-5

In 1909, S. P. L. Srenson suggested that the enormous range of concentrations of the

H3O+ and OH- ions in aqueous solutions could be compressed into a more manageable
set of data by taking advantage of logarithmic mathematics and calculating the pH or
pOH of the solution.

pH
pOH

= - log [H3O+]
= - log [OH-]

The "p" in pH and pOH is an operator that indicates that the negative of the logarithm
should be calculated for any quantity to which it is attached. Thus, pKa is the negative
of the logarithm of the acid-dissociation equilibrium constant.
pKa = - log Ka
The only disadvantage of using pKa as a measure of the relative strengths of acids is
the fact that large numbers now describe weak acids, and small (negative) numbers
describe strong acids.
HCl:
CH3CO2H:
H2O:

pKa = -3
pKa = 4.7
pKa = 15.7

KaKb = Kw = 1 x 10-14

Compound

Ka

pKa

Conjugate
Base

Kb

pKb

HI

3 x 109

-9.5

I-

3 x 10-24

23.5

HCl

1 x 106

-6

Cl-

1 x 10-20

20

H2SO4

1 x 103

-3

HSO4-

1 x 10-17

17

H3O+

55

-1.7

H2O

1.8 x 10-16

15.7

HNO3

28

-1.4

NO3-

3.6 x 10-16

15.4

H3PO4

7.1 x 10-3

2.1

H2PO4-

1.4 x 10-12

11.9

CH3CO2H

1.8 x 10-5

4.7

CH3CO2-

5.6 x 10-10

9.3

H2S

1.0 x 10-7

7.0

HS-

1 x 10-7

7.0

H2O

1.8 x 10-16

15.7

OH-

55

-1.7

CH3OH

1 x 10-18

18

CH3O-

1 x 104

-4

HC CH

1 x 10-25

25

HC C-

1 x 1011

-11

NH3

1 x 10-33

33

NH2-

1 x 1019

-19

H2

1 x 10-35

35

H-

1 x 1021

-21

CH2=CH2

1 x 10-44

44

CH2=CH-

1 x 1030

-30

CH4

1 x 10-49

49

CH3-

1 x 1035

-35

Lewis acid: An electron-pair acceptor, such as the H+ ion

The pair of electrons that went into the new covalent bond were donated by the OH- ion. Lewis therefore
argued that any substance that can act as an electron-pair donor is a Lewis base.
Lewis base: An electron-pair donor, such as the OH- ion

Reaciones de neutralizacion
2H2O= H3O++OH2NH3= NH4+NH22HF= H2F++F2SO2= SO2++SO32-

NaOH+[H3O]Cl= NaCl+2H2O
NaNH2+NH4Cl= NaCl+2NH3
NaF+[H2F]Cl= NaCl+2HF
NaF+[H2F]Cl= NaCl+2HF
Na2SO3+SOCl2= 2NaCl+2SO2

aromaticidad

Estado Solido

Solidos uno y bidimencionales

Trans-poliacetileno

b
a
a-b=
a=b
banda de conducion

calentar

banda de valencia

Cis-poliacetileno

Solidos uno y bidimencionales

Rafael Rodrigez+0.5