Chapter 8

Chapter 8
The Quantum Mechanical Atom
The Quantum Mechanical Atom
Achmad Rochliadi
Personal Use Only

Summary Highlight
Summary Highlight

Model of Atomic Theory

Electromagnetic Energy

Atomic Spectra

Matter Wave

Electron Configuration

Shape of !r"ital

Atomic propertie
Personal Use Only

Atomic Model #re $8%%
Atomic Model #re $8%%

&emocritu '

(ature of thing conit of an infinite num"er of

e)tremely mall particle* +hich they called atom,

Atom are phyically* "ut not geometrically*

indivii"le,

Atom are indetructi"le and completely full* i,e,

containing no empty pace, -ecaue of their
indetructi"ility* atom are eternal, .
Personal Use Only

&alton '

Each element i compoed of mall particle

called atom,

Atom are neither created nor detroyed in

chemical reaction,

All atom of a given element are identical

Compound are formed +hen atom of more

than one element com"ine
Personal Use Only

Thompon '

The atom of the element conit of a

num"er of negatively electrified
corpucle encloed in a phere of
uniform poitive electrification,
Personal Use Only

Rutherford

The atom of an element conit of a mall* poitively

charged nucleu in the centre* +hich carrie almot the
entire ma of the atom,

The electron are revolving around the nucleu at high

peed,

The num"er of electron in an atom i e/ual to the

num"er of proton, Hence it i electrically neutral,

The volume of the nucleu i negligi"ly mall

compared to the volume of the atom,

Mot of the pace in the atom i empty

Personal Use Only

Rutherford Simple &eign
Rutherford Simple &eign
Personal Use Only

(iel -ohr'

Atom i a mall* poitively charged nucleu

urrounded "y electron that travel in circular
or"it around the nucleu0imilar in tructure
to the olar ytem* "ut +ith electrotatic force
providing attraction* rather than gravity,
Personal Use Only

The Quantum Mechanical Atom
The Quantum Mechanical Atom

-y the late $8%%1 it +a clear that claical

phyic +a incapa"le of decri"ing atom
and molecule

E)periment ho+ed that electron acted

li2e tiny charged particle in ome
e)periment and +ave in other

The phyic that decri"e o"3ect +ith

wave/particle duality i called quantum
mechanics or quantum theory
Personal Use Only

Energy can "e tranferred "et+een thing a

light or radiation

Radiation carrie energy through pace a

waves or ocillation moving out+ard from
a ditur"ance

Electromagnetic +ave 4radiation5 may "e

characteri6ed "y their .height7 or
amplitude and the num"er that occur per
econd or frequency 4v5
Personal Use Only

11
8ight Act A A Wave
8ight Act A A Wave

Wavelength () the ditance light travel to

complete one cycle

Frequency () the num"er of +ave cycle

in one econd

unit are cycle per econd 4cp5* Hert6 4H65

H6 9
:$
Personal Use Only

Electromagnetic radiation provides the clue to the electronic structures of
atoms
12
Frequency And Wavelength Are Related
Frequency And Wavelength Are Related

(ote that a the fre/uency of the +ave

increae* the +avelength decreae

Regardle of the fre/uency* light travel at

the ame peed* c

c9;<=

the speed of light (c) 9 >,??@?>AB8 < $%

8
mC

Learning Check' Df the fre/uency of a radio

tation i E%%, MH6* +hat i the +avelength
in mF
0.999 m
Personal Use Only

7.1 Electromagnetic radiation provides the clue to the electronic structures
of atoms
13
Radiant nergy !pectrum
Radiant nergy !pectrum
high energy,
short waves
low energy,
long waves
Personal Use Only

@,$ Electromagnetic radiation provide the clue to the electronic tructure of atom $A
"hotoelectric ffect #"article $heory %f
"hotoelectric ffect #"article $heory %f
Light&
Light&

Al"ert Eintein 4$?%B5 E9h=

Shining light on a clean metal urface may

e3ect electron

There i a threhold level needed to e3ect the

electron 4a +or2 function pecific to the
metal5

Dncreaing intenity doe not caue the effect

Dncreaing the frequency of the light doe

Personal Use Only

The unit of fre/uency are the hert' 4('5

The minimum and ma)imum amplitude of

electromagnetic radiation are evenly paced

The pea2:to:pea2 ditance i called the

wavelength
5 econd C4 $ C $ $ H6 $
:$
= = =
5 4
Personal Use Only

The product of fre/uency and +avelength

give the peed of light 4c5

Electromagnetic radiation come in a "road

range of fre/uencie called the
electromagnetic spectrum

The electromagnetic pectrum i divided

into region according to the +avelength
of radiation
mC $% E,%%
8
= = c u
Personal Use Only

What +e call light i a mall lice of the

electromagnetic pectrum +ith +avelength
"et+een a"out A%% and @%% nm

Thi i called the visi)le region "ecaue +e can

.ee7 thee +avelength of the electromagnetic
pectrum

Gamma ray* H ray* and ultraviolet radiation

have +avelength horter than the vii"le region

Micro+ave* infrared radiation* and radio +ave

have +avelength longer than vii"le light
Personal Use Only

The +ay a u"tance a"or"

electromagnetic radiation can "e ued to
characteri6e it

Ior e)ample* each u"tance a"or" a

uni/uely different et of infrared
fre/uencie

A plot of +avelength a"or"ed veru the

a"orption i called an infrared a)sorption
spectrum

Dt can "e ued to identify a u"tance

Personal Use Only

The ocillating magnetic and electric field

of an electromagnetic +ave interact +ith
particle that it pae

A charged particle can pic2 up energy at the

e)pene of the radiation ource
Infrared
asorption
spectrum
of wood
alcohol
!methanol"
.
Personal Use Only

The energy tranfer i not decri"e correctly

"y claical phyic

Dn $?%% the German cientit Ma) #lanc2

propoed that the electromagnetic radiation
could "e vie+ed a a tream of tiny energy
pac2et or quanta +e no+ call photons

#hoton travel at the peed of light

#lanc2 propoed* and Eintein confirmed*

that the energy of a photon is proportional
to its frequency
Personal Use Only

Thi mean that )oth electron and

electromagnetic radiation can "e
repreented a either +ave or particle

The vii"le pectrum i a continuous

pectrum "ecaue it contain a continuou
ditri"ution of light of all color

E)cited atom can emit light

J $% K,K>K contant #lanc2L
photon of energy
EA :
= =
= =
h
h E v
Personal Use Only

>>
Ilame Emiion
Ilame Emiion

Element e)hi"it characteritic color +hen

"urned

The characteritic pectra are alo o"erved

+hen element are u"3ect to trong electrical
field a in ga dicharge tu"e,
(ote that the
light from the
dicharge tu"e i
actually everal
different colored
line a een on
the urface of the
C&
Personal Use Only

The atomic spectrum or emission

spectrum i a erie of individual line
called a line spectrum

Atomic pectra are uni/ue for each element

#ight emitted y
e$cited atoms is
comprised of a
few narrow eams
with fre%uencies
characteristic of
the element.
Personal Use Only

Dn general* the line pectrum of an element

i rather complicated

The line pectrum of hydrogen* +ith a

ingle electron* i the implet

The Ryd)erg equation can "e ued to

calculated all the pectral line of hydrogen
n
1
and n
>
are poitive integers
#attern Dn Atomic 8ine Spectra
$

=R
H
(
$
n
$
>

$
n
>
>
)
Personal Use Only

The Ryd"erg contant* R
H
* i an empirical
contant +ith a value of $%?*K@8 cm
:$

Atomic line pectra tell u that when an

excited atom loses energy, not just any
arbitrary amount can be lost

Thi i poi"le if the electron i retricted

to certain energy levels

The energy of the electron i aid to "e

quanti'ed
Personal Use Only

The firt theoretical model that uccefully

accounted for the Ryd"erg e/uation +a
propoed in $?$E "y (iel -ohr
&ontinuous !a" and discrete
!" potential energy of a
tortoise. 'he potential energy
of the tortoise in !" is
%uanti(ed.
Personal Use Only

@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie >8

Electron move around the nucleu in fi)ed

path or orbits much li2e the planet move
around the un

!r"it poition* la"eled +ith the integer n*

have pecific potential energy

The lo+et energy tate of an atom i called

the ground state 4an electron +ith n 9 $ for a
hydrogen atom5
-ohr1 Model !f The Atom
-ohr1 Model !f The Atom
Personal Use Only

@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie >?
A"orption And Emiion
A"orption And Emiion

Electron that
absorb energy are
raied to a higher
energy level

A particular
fre/uency of light i
emitted +hen an
electron fall to a
lo+er energy level
Personal Use Only

@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie E%

Thi e/uation allo+ the calculation of the energy*

E* of any or"it

"9 -ohr1 contant

n i the or"it location

J $% >,$8 "
n
"
E
$8
>

=
=
-ohr E/uation 4$?$E5
-ohr E/uation 4$?$E5
Personal Use Only

@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie E$

-ohr1 4theoretical5 e/uation e)plain the

e)perimental 4empirical5 Ryd"erg e/uation

The com"ination of contant* b/hc* ha a

value +hich differ from the e)perimentally
derived value of R
H
"y only %,%BMN
( )
( ) ( )
> >
> >
> >
$ $ $ $
$ $
or
+ith
5 4
h l
h l
l h
n n
hc
b
l h
n n
n
b
n
b
l h
hc
n n b
E E E
= =
> =
= = A


-ohr1 Model #redict Energy 8evel
-ohr1 Model #redict Energy 8evel
Personal Use Only

@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie E>
Oour TurnN
Oour TurnN
Which energy i not poi"le according to -ohr1
ModelF
A, :B,B<$%
:$?
J
-, :$,A<$%
:$?
J
C, :$,8<$%
:$?
J
&, none of thee
Personal Use Only

@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie EE

Theory +a not
a"le to e)plain
the pectra of
atom +ith more
than one electron

Theory doen1t
e)plain the
collaping atom
parado)
-ohr1 Model Iail
-ohr1 Model Iail
Personal Use Only

@,E Electron have propertie of "oth particle and +ave EA
8ight E)hi"it Dnterference
8ight E)hi"it Dnterference

Constructive interference: +ave .in:

phae7 create +ave of greater amplitude
4 they add5

estructive interference: +ave .out:of:

phae7 create +ave of lo+er amplitude
4they cancel out5
Personal Use Only

@,E Electron have propertie of "oth particle and +ave EB

8ight e)hi"it interference* and it alo ha

particle nature

Electron* 2no+n to "e particle* alo

demontrate interference
&iffraction And Electron
&iffraction And Electron
Personal Use Only

Personal Use Only

An electron that .ecape7 from the nucleu

ha infinity for it /uantum num"er and
6ero energy

-ohr1 4theoretical5 e/uation e)plain the

4empirical5 Ryd"erg e/uation
( )
( ) ( )
> >
> >
> >
$ $ $ $
$ $
or
+ith
5 4
h l
h l
l h
n n
hc
b
l h
n n
n
b
n
b
l h
hc
n n b
E E E
= =
> =
= = A


Personal Use Only

The com"ination of contant* b/hc* ha a

value +hich differ from the e)perimentally
derived value of R
H
"y only %,%BM

-ohr1 effort to develop a general theory

of electronic tructure +a doomed "y the
+aveCparticle duality of electron

&e -roglie uggeted that the +avelength

of a particle of ma m moving at peed v i
mv
h
=
Personal Use Only

Thi relation provide the lin2 "et+een the

decription a a particle and a a +ave

Heavy o"3ect have very .hort7

+avelength o their matter +ave and the
+ave propertie go unnoticed

Tiny particle +ith mall mae have

.long7 +avelength o their +ave propertie
are an important part of their "ehavior

Wave com"ine in t+o +ay

Personal Use Only

The contructive and detructive

interference i called diffraction

Electron produce imilar pattern

!a" )aves in phase interfere constructively. !" *ut of phase
waves produce destructive interference. !c" )aves passing
through holes fan out and produce an interference pattern.
Personal Use Only

There are t+o type of +ave' traveling

and standing

A tanding +ave i produced +hen a guitar

tring i pluc2ed' the center of the tring
vi"rate* "ut the end remain fi)ed

#oint of 6ero +ave amplitude are called

nodes
'he wind produces
traveling waves on the
surfaces of la+es and
oceans.
Personal Use Only

Ior guitar tring the only +ave are thoe

for +hich a half:+avelength i repeated
e*actly a +hole num"er of time

Ior a trength of length +ith n an integer

thi can "e +ritten
,tanding waves on a guitar
string.
( )
n

n
>
>
' g rearrangin or = =

Personal Use Only

Thee reult can "e ued to ho+ ho+

/uantum theory unite the +ave and particle
decription of a "ound electron

Conider the claical particle model of the

."ead on a +ire7

Df the electron 4particle5 ha ma m and

peed v

The 2inetic energy of the moving electron i

>
>
$
mv E =
Personal Use Only

The &e -roglie relation connect model

4a5 and 4"5
!a" - classical model of the
electron as a ead on a wire. -ny
energy is possile and position is
e$actly +nown. !" &lassical
model of the electron as a
standing wave. !c" .uantum
mechanical model comines !a"
and !". /ar+ areas indicate
proale electron positions.
Personal Use Only

Personal Use Only

The electron energy i /uanti6ed "ecaue it

depend on the integer n

The lo+et energy allo+ed i for n9$ or

E!h
"
/#m
"
4the energy cannot )e 'ero5
( )
>
>
>
>
>
8
>
>
>
>
$
>
>
$
give uing
' ng u"tituti or
m
h n
n

m
h
m
h
m
h
mv
h
E
m mv E
v
= =
= = =
= =

Personal Use Only

Electron trapped on a +ire have ome

reidual 2inetic energy* 3ut li2e electron
trapped in atom
'he spacing
etween levels is
proportional to 10#
2
.
!a" - long wire. !"
- short wire. 'he
longer the wire, the
smaller the spacing
etween allowed
energy levels.
Personal Use Only

The +ave that correpond to the electron i

called a wave function

The amplitude of the +ave function at a

given point can "e related to the
pro)a)ility of finding the electron there

According to /uantum mechanic there are

region of the +ire +here the electron +ill
not "e found

Region of 6ero +ave function amplitude

are called node
Personal Use Only

Dt i generally true that the more nodes an

electron has, the higher its energy

Er+in SchrPdinger +a the firt to

uccefully apply the concept of the +ave
nature of matter to electronic tructure

He developed an e/uation that can "e

olved to give +ave function and energy
level for electron trapped in them

Wave function for electron in atom are

called or)itals
Personal Use Only

!r"ital are characteri6ed "y a et of three

/uantum num"er'
n 9 principle /uantum num"er, All
or"ital +ith the ave principle
/uantum num"er are in the ame shell,
Allo+ed value' the et of poitive
integer,
l 9 econdary /uantum num"er +hich
divide the or"ital in a hell into
maller group called su)shells,
Allo+ed value' from % to 4n Q $5,
m
l
9 magnetic /uantum num"er +hich
divide the u"hell into individual
or"ital, Allo+ed value' integer from
Ql to Rl,
Personal Use Only

1elationships etween n, l, and m
l
.
2umer of
n l m
l
,ushell *ritals

1 0 0 1s 1
2 0 0 2s 1
1 31, 0, 1 2p 3
3 0 0 3s 1
1 31, 0, 1 3p 3
2 32, 31, 0, 1, 2 3d 4
5 0 0 5s 1
1 31, 0, 1 5p 3
2 32, 31, 0, 1, 2 5d 4
3 33, 32, 31, 0, 1, 2, 3 5f 7
Personal Use Only

The appro)imate energie of the u"hell

in an atom +ith more than one electron'

Electron "ehave li2e tiny magnet

'he %uantum
numers
associated with
the first two
shells are
shown.
Personal Use Only

Electron +ithin atom interact +ith a

magnet field in one of t+o +ay'

Electron pin i important in determining

electronic tructure
Electrons can spin in either
direction in the presence of an
e$ternal magnetic field. 'his
gives rise to the spin %uantum
numer, m
s
with allowed
values of 6102 !spin 7up8" or 9
102 !spin 7down8".
Personal Use Only

According to the "auli e*clusion principle

no two electrons in the same atom can have
identical values for all four quantum
numbers

Thu t+o electron can occupy the ame

or"ital only if they have oppoite pin and
are aid to "e paired

A u"tance +ith more pin in one direction

i aid to contain unpaired electron
Personal Use Only

Su"tance +ith unpaired electron are

lightly attracted to a magnet and are called
paramagnetic

Su"tance in +hich all electron are paired

are called diamagnetic

The ditri"ution of electron among the

or"ital of an atom i called the electronic
structure or electronic configuration
Personal Use Only

To indicate the ground tate electron

configuration +e can'
$5 8it the u"hell that contain electron and
indicate their electron population +ith a
upercript,
>5 Repreent each or"ital +ith a circle and ue
arro+ to indicate the pin of each electron,

Electron configuration mut "e conitent

+ith the #auli principle* auf"au principle*
and Hund1 rule
E)ample' ( $s
>
>s
>
>p
E
* (a $s
>
>s
>
>p
K
Es
$
Personal Use Only

Electron configuration e)plain the

tructure of the periodic ta"le
'he periodic tale is
divided into regions
of 2, :, 10, and 15
columns which is
the ma$imum
numer of electrons
in s, p, d, and f
sulevels.
,ushells that fill
across the periods.
Personal Use Only

Ior the repreentative element 4A Group5

the electron +ith the highet n value or
valence shell are normally the only
electron important for chemical propertie

Ior thee element the valence electrons

consist of just the s and p subshells
encountered crossing the period that
contains the element in question
E)ample' the valence configuration of
"romine i
-r As
>
Ap
B

Personal Use Only

There are fe+ important e)ception to the

.e)pected7 electronic figuration of
commonly encountered element

Iollo+ing the rule for Cr* Cu* Ag* and Au

uing no"le ga notation'
$ $% > ?
$ $% > ?
$ $% > ?
$ B > A
K SHeTB K SHeTB Cu
B SUrTA B SUrTA Ag
A SArTE A SArTE Cu
A SArTE A SArTE Cr
al E)periment E)pected Element
s d s d
s d s d
s d s d
s d s d
Personal Use Only

Apparently* half:filled and filled u"hell

are particularly ta"le

Similar irregularitie occur among the

lanthanide and actinide element

The poition of an electron mut "e

decri"ed +ith pro"a"ilitie

Heien"erg1 uncertainty principle ay

that it i impoi"le to meaure +ith
complete preciion the velocity and
poition of a particle imultaneouly
Personal Use Only

Thee limitation are not important for large

o"3ect "ut are very important for mall
particle li2e electron

Quantum mechanic re/uire that +e tal2

a"out the pro"a"ility of finding an electron
in a particular region of pace

Thi pro"a"ility i often repreented a an

electron cloud a"out the nucleu

The pro"a"ility varie +ith ditance from

the nucleu
Personal Use Only

Thi type of plot ho+ that electron

density varie from place to place

Electron denity variation define the hape*

i6e* and orientation of or"ital
!a" - dot3density
diagram for an
electron in a 1s
orital. !" ;raph
of proaility
versus distance.
Personal Use Only

p or"ital are /uite different from s or"ital

They poe a nodial plane +hich include

the nucleu and eparate the .lo"e7 of
high pro"a"ility
*ritals get larger as the
principle %uantum numer n
increases. 2odes, or regions
of (ero electron density,
appear eginning with the 2s
orital.
Personal Use Only

Recall that there are three different or"ital

in each p u"hell
/ot3density diagrams of
the cross section of the
proaility distriution of a
single !a" 2p and !" 3p
orital showing the nodal
plane.
'he directions of ma$imum electron
density lie along lines that are
mutually perpendicular. It is
convenient to lael the oritals as p
$
,
p
y
, and p
(
Personal Use Only

The hape and orientation of d or"ital are

more complicated than for p or"ital
Shape and directional propertie of the
five d or"ital in a d u"hell,

The f or"ital are even more comple) than

the d or"ital
Personal Use Only

The amount of poitive charge .felt7 "y

outer electron in atom other than
hydrogen i called the effective nuclear
charge

Dt i lo+er than the atomic num"er "ecaue

of shielding
If the 23 charge of the
1s
2
core of lithium were
100< effective at
shielding the 2s electron
from the nucleus, the
valence electron would
7see8 a charge of 61.
Personal Use Only

The effective nuclear charge felt "y outer

electron i determined primarily "y the
difference "et+een the charge on the
nucleu and the charge on the core

Effective nuclear charge control a num"er

of propertie

Atomic i6e increae top to "ottom in a group

"ecaue of increaing n and get maller left to
right in a group "ecaue the effective nuclear
charge increae
Personal Use Only

Variation in atomic and ionic radii, Value

in picometer 4$%
:$>
m5
Personal Use Only

The i6e trend in ion can "e ummari6ed'

#oitive ion are al+ay maller than the atom

they are formed

(egative ion al+ay larger than the atom

from +hich they are formed
-dding electrons leads to
an increase in si(e of a
particle, as illustrated for
fluorine. 1emoving electrons
decreases the si(e of the
particle, as shown for
lithium and iron.
Personal Use Only

+oni'ation energy 4DE5 i the energy

re/uired to remove an electron from an
iolated* gaeou atom

Succeive ioni6ation are poi"le until no

electron remain

The trend in DE are the oppoite of the

trend in atomic i6e
+
+ e g $ g $ 5 4 5 4
Personal Use Only

=ariations in first
ioni(ation3energies.
Elements with the
largest ioni(ation
energies are in the
upper right of the
periodic tale. 'hose
with the smallest
ioni(ation energy are
at the lower left.
Personal Use Only

=ariations in
successive
ioni(ation
energies. 2ote
that it is
e$tremely
difficult to rea+
into the nole
gas core !2
nd

through >
th

ioni(ations for #i
through ?,
respectfully.
Personal Use Only

The electron affinity 4EA5 i the potential

energy change aociated +ith the addition
of an electron to a gaeou atom or ion in it
ground tate

The addition of one electron to a neutral

atom i e)othermic for nearly all atom

The addition of more electron re/uire

energy
5 4 5 4 g $ e g $

+
Personal Use Only

Conider the addition of electron to

o)ygen'

The reult for firt electron affinitie can

"e generali6ed
: :
: : >:
: >:
Change EA42JCmol5
!4g5 e ! 4 5 :$A$
! 4g5 e ! 4 5 8AA
(et' !4g5 >e ! 4 5 @%E
g
g
g
+
+ +
+ +
Personal Use Only

Dn general'

EA increae from left to right in a period

EA increae "ottom to top in a group

Personal Use Only

Meauring atomic mae
Meauring atomic mae
Personal Use Only