Mecnica cuntica

Mecnica Cuntica
Es una descripcin matemtica de los enlaces que toma
en cuenta la naturaleza ondulatoria del electrn.
Una ecuacin de onda se resuelve para producir una
serie de funciones de onda para el tomo.
Las funciones de onda psi () describen una serie de
estados con diferentes energas para cada electrn.
Estas ecuaciones se utilizan para calcular:
La energia asociada con e estado de un electron
La probabilidad de encontrar un electron en un estado
particular

 Signos de fase: las ecuaciones de onda pueden ser

positivas negativas o cero.
En analoga a la onda de un lago, cuando esta sobre el
nivel es positiva( = +) , cuando esta bajo el nivel
negativa( = - )
Cuando la onda tiene el nivel del lago es igual a ceroy se
llama un nodo ( = 0)

Wave equations can reinforce each other if they

have the same sign or interfere with each other if
they have different signs
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 Orbitales Atmicos
2 da la probabilidad de encontrar un electrn en
una ubicacin particular en el espacio
Los grficos de 2 en 3 D generan la forma de los
orbitales s, p, d y f
Solo los orbitales s y p son muy importantes en
qumica orgnica
Orbital: una regin en el espacio donde la
probabilidad de encontrar un electrn es grande
La tpica representacin de los orbitales son aquellos que
contienen el 90-95% del tiempo

 Los orbitales 1s y 2s son esferas alrededor del ncleo

Cada orbital puede contener 2 electrones

Cada orbital 2p tiene dos esferas que casi se tocan

Hay tres orbitales 2p perpendiculares entre si
Los tres orbitales son degenerados (= E)

Los orbitales 2p son de mas alta energa que 1s o 2s

El signo de la funcin de onda no indica mayor o menor probabilidad

de encontrar un electrn.
Mientras mayor sea el numero de nodos mayor es la energa del
orbital.
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 La configuracin electrnica de los tomos se puede

realizar siguiendo las siguientes reglas:
Principio Aufbau: los orbitales de menor energa se llenan
primero
Principio de exclusin de Pauli: en cada orbital se puede
colocar un mximo de 2 electrones ()
Regla de Hund: cuando se tienen orbitales de igual energa
(degenerados) como los p, se agrega un electrn a cada uno
de los orbitales. Luego se agrega un segundo electrn.

Configuracin electrnica de elementos de la segunda

fila

 Orbitales moleculares
Un modelo simple de los enlaces se ilustra con la formacin
de H2 a partir de tomos de H y distancias variables:

 Este modelo no toma en cuenta el hecho de que los

electrones se encuentran en constante movimiento.
El principio de incertidumbre de Heisenberg: la posicin y el
momento de un electrn no puede ser determinado en forma
simultanea.

Este problema se resuelve describiendo la probabilidad ( 2)

de encontrar un electrn en una ubicacin en el espacio.
Al acercarse dos electrones a sus orbitales atmicos estos se
sobrelapan formando un orbital molecular.
Estos abarcan los ncleos y los electrones se mueven
alrededor de ambos.
El numero de OM es igual al numero de OA que lo forman.

 Example: H2 molecule
As the hydrogen atoms approach each other their 1s orbitals
(1s) begin to overlap
The MOs that form encompass both nuclei
The electrons are not restricted to the vicinity of one nucleus
or another
Each MO has a maximum of 2 spin-paired electrons
Addition of wave functions of the two atoms leads to a
bonding molecular orbital
Subtraction of wave functions of the two atoms leads to an
anti-bonding molecular orbital
The mathematic operation by which wave functions are added
or subtracted is called the linear combination of atomic
orbitals (LCAO)

ORBITALES MOLECULARES
Orbitales moleculares enlazantes (molec)
Los OAs se combinan por adicin (los OAs del mismo signo de fase se
superponen)
Las funciones de onda se refuerzan
El valor de aumenta entre los dos ncleos
El valor de 2 (electron probability density) en la regin entre los dos
nucleos
Los dos electrones atraen a los dos ncleos acercndolos entre si.
Este es el estado fundamental del OM (estado de menor energa)

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 Orbital molecular antienlazante ( *molec)

Formado por la interaccin de OAs con signos de fase opuestas
Las funciones de onda interfieren y se produce un nodo ( = 0)
En la regin entre ambos nucleos
Se produce un nodo
A cada lado del nodo es pequea
2 (electron probability density) es pequea

Los electrones del orbital antienlazante evitan la regin entre los

ncleos
Fuerzas repulsivas entre los ncleos predominan predominante y los
electrones en *molec hacen que los ncleos se alejen

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 La energa de los electrones en los orbitales enlazantes es sustancialmente

menor a la energa de los electrones en tomos individuales.
En el estado fundamental de la molecular de hidrogeno los electrones ocupan
el orbital enlazante de menor energa

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Enlaces sigma()

La densidad electrnica se encuentra entre los ncleos.

Un enlace puede estar formado por orbitales s-s, p-p, s-p, u
orbitales hbridos que se superpone.

Enlaces Pi ()
Los enlaces Pi () se forman despus de los enlaces sigma.
Ocurren por solapamiento lateral de orbitales p paralelos

Enlaces mltiples
Un doble enlace (2 pares de electrones compartidos) consiste en un enlace
sigma y un enlace pi.
Un enlace triple (3 pares de electrones compartidos) consiste en un enlace
sigma y dos enlaces pi.

=>

Los ngulos de enlace no se pueden explicar con orbitales s o p

simples. Utilice la teora RPECV. (repulsin de electrones de valencia)
los orbitales hbridos son ms bajos en energa, porque los pares de
electrones estn ms alejados.
La hibridacin es la combinacin de orbitales atmicos (CLOA) dentro
de un tomo, justo antes de la unin.
Revisaremos esta situacin analizando algunos compuestos orgnicos

 La estructura del metano y el etano: hibridacin sp3

La estructura tetradrica del metano no se puede explicar usando la
configuracin electrnica del carbono

La hibridacin de los orbitales de valencia (2s and 2p) produce

cuatro orbitales idnticos, usados en los enlaces del metano
La hibridacin de orbitales es la media de las funciones de onda de
los orbitales 2s y 2p involucrados.
Cuando un orbital 2s y tres 2p se hibridan, se obtienen cuatro
orbitales sp3
una parte s y tres p
Orientacin tetradrica

Los orbitales sp3 se combinan con los orbitales 1s de cuatro

hidrgenos para obtener le metano
Cada orbital molecular puede tener dos electrones

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 Un orbital sp3 se asemeja a un orbital p con un lbulo extendido

Often the small lobe is not drawn

El lobulo extendido del sp3 se puede sobrelapar con el orbital 1s del

hidrogeno formando un enlace fuerte.

El enlace formado es llamado sigma ()

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 A variety of representations of methane show its tetrahedral nature

and electron distribution
a. calculated electron density surface b. ball-and-stick model c. a typical
3-dimensional drawing

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 Etano (C2H6)
El enlace carbono-carbono se forma del sobrelapamiento de dos
orbitales sp3 orbitales para formar un enlace
La molcula es aproximadamente tetradrica alrededor de cada
carbono

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 La representacin del etano muestra el ordenamiento

tetradrico alrededor de cada carbono
a. calculated electron density surface b. ball-and-stick model c. typical 3dimensional drawing

Generalmente hay una rotacin relativamente libre en los

enlaces sigma

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 La estructura del Eteno (Etileno) : hibridacin sp2

El eteno (C2H2) contiene un doble enlace carbono-carbono, es de los
compuestos orgnicos llamados alquenos
Otro ejemplo de alquenos es el propeno

La geometria alrededor de cada carbono se llama trigonal planar

Todos los atomos conectados directamente conectados a cada carbono
estan en el mismo plano
Los enlances apuntan hacia los extremos de un triangulo
El angulo de enlace es aproximadamente 120o

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 Hay tres enlaces alrededor de cada carbono del eteno y y se

forma usando orbitales hibridos sp2 hybridized orbitalsThe
three sp2 hybridized orbitals come from mixing one s and two
p orbitals
Un orbital p orbital permanece sin hibridar

Los orbitales sp2 se ordenan en un plano trigonal

El orbital p es perpendicular (orthoganol) al plano

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 Overlap of sp2 orbitals in ethylene results in formation of a framework

One sp2 orbital on each carbon overlaps to form a carbon-carbon bond; the
remaining sp2 orbitals form bonds to hydrogen

The leftover p orbitals on each carbon overlap to form a bonding bond

between the two carbons
bond results from overlap of p orbitals above and below the plane of the
bond
It has a nodal plane passing through the two bonded nuclei and between the two
lobes of the molecular orbital

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 The bonding orbital results from overlap of p orbital lobes of the same sign
The antibonding * orbital results from overlap of p orbital lobes of opposite
sign
The antibonding orbital has one node connecting the two nuclei and another node
between the two carbons

The bonding orbital is lower in energy than the antibonding orbital

In the ground state two spin paired electrons are in the bonding orbital
The antibonding *orbital can be occupied if an electron becomes promoted from
a lower level ( e.g. by absorption of light)

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 The orbital is lower in energy than the orbital

The ground state electronic configuration of ethene is shown

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 Restricted Rotation and the Double Bond

There is a large energy barrier to rotation (about 264 kJ/mol) around
the double bond
This corresponds to the strength of a bond
The rotational barrier of a carbon-carbon single bond is 13-26 kJ/mol

This rotational barrier results because the p orbitals must be well

aligned for maximum overlap and formation of the bond
Rotation of the p orbitals 90o totally breaks the bond

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 Cis-trans isomers
Cis-trans isomers are the result of restricted
rotation about double bonds
These isomers have the same connectivity of atoms
and differ only in the arrangement of atoms in
space
This puts them in the broader class of stereoisomers

The molecules below do not superpose on each

other
One molecule is designated cis (groups on same
side) and the other is trans (groups on opposite
side)

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 The Structure of Ethyne (Acetylene): sp

Hybridization
Ethyne (acetylene) is a member of a group of
compounds called alkynes which all have carboncarbon triple bonds
Propyne is another typical alkyne

The arrangement of atoms around each carbon is

linear with bond angles 180o
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 The carbon in ethyne is sp hybridized

One s and one p orbital are mixed to form two sp orbitals
Two p orbitals are left unhybridized

The two sp orbitals are oriented 180o relative to

each other around the carbon nucleus
The two p orbitals are perpendicular to the axis that
passes through the center of the sp orbitals

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 In ethyne the sp orbitals on the two carbons

overlap to form a bond
The remaining sp orbitals overlap with hydrogen 1s
orbitals

The p orbitals on each carbon overlap to form two

bonds
The triple bond consists of one and two bonds

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 Depictions of ethyne show that the electron density

around the carbon-carbon bond has circular
symmetry
Even if rotation around the carbon-carbon bond occurred,
a different compound would not result

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 Bond Lengths of Ethyne, Ethene and Ethane

The carbon-carbon bond length is shorter as more
bonds hold the carbons together
With more electron density between the carbons, there is
more glue to hold the nuclei of the carbons together

The carbon-hydrogen bond lengths also get shorter

with more s character of the bond
2s orbitals are held more closely to the nucleus than 2p
orbitals
A hybridized orbital with more percent s character is held
more closely to the nucleus than an orbital with less s
character
The sp orbital of ethyne has 50% s character and its C-H
bond is shorter
The sp3 orbital of ethane has only 25% s character and its
C-H bond is longer
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 Summary of Concepts from Quantum

Mechanics
Atomic Orbital(AO): region in space around a
nucleus where there is a high probability of
finding an electron
Molecular Orbital (MO): results from overlap of
atomic orbitals
Bonding Orbitals: when AOs of same sign
overlap

Antibonding Orbitals: when AOs of opposite

sign overlap

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 The number of molecular orbitals formed

equals the number of the atomic orbitals used
Hybridized orbitals are obtained by mixing the
wave functions of different types of orbitals
Four sp3 orbitals are obtained from mixing one s
and three p orbitals
The geometry of the four orbitals is tetrahedral
This is the hybridization used in the carbon of methane

Three sp2 orbitals are obtained from mixing one s

and two p orbitals
The geometry of the three orbitals is trigonal planar
The left over p orbital is used to make a bond
This is the hybridization used in the carbons of ethene

Two sp orbitals are obtained from mixing one s and

one p orbital

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 Molecular Geometry: The Valence Shell

Electron Pair Repulsion (VSEPR) Model
This is a simple theory to predict the geometry of
molecules
All sets of valence electrons are considered
including:
Bonding pairs involved in single or multiple bonds
Non-bonding pairs which are unshared

Electron pairs repel each other and tend to be as far

apart as possible from each other
Non-bonding electron pairs tend to repel other
electrons more than bonding pairs do (i.e. they are
larger)
The geometry of the molecule is determined by the 37
number of sets of electrons by using geometrical

 Methane
The valence shell of methane contains four pairs or
sets of electrons
To be as far apart from each other as possible they
adopt a tetrahedral arrangement (bond angle
109.5o)
The molecule methane is therefore tetrahedral

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 Ammonia
When the bonding and nonbonding electrons are
considered there are 4 sets of electrons
The molecule is essentially tetrahedral but the
actual shape of the bonded atoms is considered to
be trigonal planar
The bond angles are about 107o and not 109.5o
because the non-bonding electrons in effect are
larger and compress the nitrogen-hydrogen bond

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 Water
There are four sets of electrons including 2 bonding
pairs and 2 non-bonding pairs
Again the geometry is essentially tetrahedral but
the actual shape of the atoms is considered to be
an angular arrangement
The bond angle is about 105o because the two
larger nonbonding pairs compress the electrons
in the oxygen-hydrogen bonds

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 Boron Trifluoride
Three sets of bonding electrons are farthest apart in
a trigonal planar arrangement (bond angle 120o)
The three fluorides lie at the corners of an equilateral
triangle

Beryllium Hydride
Two sets of bonding electrons are farthest apart in a

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 Carbon Dioxide
There are only two sets of electrons around the
central carbon and so the molecule is linear (bond
angle 180o)
Electrons in multiple bonds are considered as one set of
electrons in total

A summary of the results also includes the

geometry of other simple molecules
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 Representations of Structural Formulas

Dot formulas are more cumbersome to draw than
dash formulas and condensed formulas
Lone-pair electrons are often (but not always)
drawn in, especially when they are crucial to the
chemistry being discussed

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 Dash formulas
Each dash represents a pair of electrons
This type of representation is meant to emphasize
connectivity and does not represent the 3dimensional nature of the molecule
The dash formulas of propyl alcohol appear to have 90o
angles for carbons which actually have tetrahedral bond
angles (109.5o)

There is relatively free rotation around single bonds

so the dash structures below are all equivalent

Constitutional isomers
Constitutional isomers have the same molecular formula

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 Condensed Structural Formulas

In these representations, some or all of the dash
lines are omitted
In partially condensed structures all hydrogens
attached to an atom are simply written after it but
some or all of the other bonds are explicitly shown
In fully condensed structure all bonds are omitted
and atoms attached to carbon are written
immediately after it
For emphasis, branching groups are often written
using vertical lines to connect them to the main
chain

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 Bond-Line Formulas
A further simplification of drawing organic
molecules is to completely omit all carbons and
hydrogens and only show heteroatoms (e.g. O, Cl,
N) explicitly
Each intersection or end of line in a zig-zag
represents a carbon with the appropriate amount
of hydrogens
Heteroatoms with attached hydrogens must be drawn in
explicitly

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 Cyclic compounds are condensed using a drawing of

the corresponding polygon

Multiple bonds are indicated by using the

appropriate number of lines connecting the atoms

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 Three-Dimensional Formulas
Since virtually all organic molecules have a 3dimensional shape it is often important to be able
to convey their shape
The conventions for this are:
Bonds that lie in the plane of the paper are indicated by a
simple line
Bonds that come forward out of the plane of the paper
are indicated by a solid wedge
Bonds that go back out of the plane of the paper are
indicated by a dashed wedge

Generally to represent a tetrahedral atom:

Two of the bonds are drawn in the plane of the paper
about 109o apart
The other two bonds are drawn in the opposite direction
to the in- plane bonds but right next to each other
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 Trigonal planar arrangements of atoms can be

drawn in 3-dimensions in the plane of the paper
Bond angles should be approximately 120o
These can also be drawn side-on with the central bond in
the plane of the paper, one bond forward and one bond
back

Linear arrangements of atoms are always best

drawn in the plane of the paper

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