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|   

Ô    

Ô
u  
ë Discovered by accident
ë Becquerel

ë Three types
ë alpha
alpha-- helium nucleus (+2 charge, large
mass)
ë beta
beta-- high speed electron
ë gamma
gamma-- high energy light
u
  


ë
sed helium to produce alpha particles.
ë Aimed alpha particles at gold foil by drilling a
hole in a lead block.
ë Since the mass is evenly distributed in gold
atoms, alpha particles should go straight
through.
ë
sed gold foil because it could be made
atoms thin.

 
º 
  



 









What he expected
Varticles would pass through

`  
`      
  
    

?ass was evenly distributed


What he got
wow he explained it

ë Atom is mostly empty


ë Small dense, positive
½
piece at center.
ë Alpha particles
are deflected by it if they
get close enough.
 u
 



½
Ô
 


ë Dalton
ë Smallest indivisible particle

ë Thomson
ë Included the electron into the atom

ë Rutherford
ë Nuclear atom with a layer of electrons.
Ô



ë The atom is mostly


empty space.
ë Two regions
ë Nucleus
Nucleus-- protons and
neutrons.
ë Electron cloud-
cloud- region
where you might find an
electron.
Ôax Plank added a twist
with his Quantum Theory

In 1900, Plank proposed that:




   
  

   

   

    
 


  
 

 !  
In order for an atom to absorb a packet of energy, it
must absorb the whole packet or none at all.
G G  

Plank's

critics were legion. It wasn't until
1902 that a young man who worked at a
telegraph office near Berlin designed an
experiment that would be known as the
"Photoelectric Effect".
This young man was Albert Einstein.



In his experiment Einstein showed that as the
frequency of radiation was directly proportional to
the energy that was absorbed by the electrons.
The math statement of this relationship is stated as
:

E = hu

here E is the energy, absorbed by the electrons, h


is Plank·s Constant and u is frequency of radiation.
ºº
Ú
"  



"  
  !  


u
   

" #
 

[ e proposed that the electrons existed at


set levels of energy, at fixed distances
from the nucleus.
nucleus.
[ If the atom absorbed energy, the
electron jumped to a level further from
the nucleus
" #
 

[ If it radiated energy, it fell to a level


closer to the nucleus.
nucleus.
[ is model was a huge leap forward in
making theory fit the experimental
evidence that other physicists had
found over the years.
years.
#
" Ô
 


ë Nucleus ë In the center, contains protons & neutrons

ë Protons ë positive, one atomic mass unit (amu)

ë Neutrons ë neutral, one amu

ë Shells ë energy levels around nucleus

ë Electrons ë negative, no effective mass


#
" Ô
 


a
a a
a
V
 
  
a a
 
 



a
a
a a
#
" Ô
 


ë The atomic number (å


(å) is the number of
protons in an atom
ë Each element has a unique atomic number
or
ë Each element has a different number of protons
[ hen the light is passed through a prism only a
few wavelengths are present in resulting spectra

[ These appear as lines separated by dark areas,


and thus are called line spectra

[ hen the spectrum emitted by hydrogen gas was


passed through a prism and separated into its
constituent wavelengths four lines appeared at
characteristic wavelengths
[ Bohr began with the assumption that electrons
were orbiting the nucleus, much like the earth
orbits the sun.

[ rom classical physics, a charge traveling in a


circular path should lose energy by emitting
electromagnetic radiation
[ If the "orbiting" electron loses energy, it should
end
up spiraling into the nucleus (which it does not).

[ Therefore, classical physical laws either don't apply


or are inadequate to explain the inner workings of
the atom
[ Bohr borrowed the idea of quantize energy from
Planck

[ e proposed that only orbits of certain radii,


corresponding to defined energies, are "permitted"

[ An electron orbiting in one of these "allowed" orbits:

[ as a defined energy state

[ ill not radiate energy


[ ill not spiral into the nucleus
If the orbits of the electron are restricted,
the energies that the electron can possess are
likewise restricted and are defined by the
equation:
Bohr Ôodel of the atom

 Ô    Ôi Ô
  u  Ô    u  Ô  u 
£
Ô
@
@  @  i  aÔ

 @@ÔM
u # M    MÔ$

]      


å    
  
M    
a  !" 
 
Ô 
 
 
@ x xx G  %x G G @ ·    & 
@ 
@ &'ë
G *#
@ (    
G& * M#
@ &(  )    
G *#
@ ( )    
G+ *M#

G *M+#
,
,
,
Gë M#
ë ƒohann Rydberg, 19th century spectroscopic
ë All wavelengths (ƫ
(ƫ, lambda) can be described

§ R is Rydberg constant, 1.097 x 107 m-1


§ n are integers; n1 = 1,2«. and n2 = n1 + 1, n1 + 2«.
§ Series with n1 = 1 lies in ultraviolet region
, ºy?an series

§ Series with n1 = 2 lies in visible region


, `al?er series

§ Infrared series includes:


, Paschen series (n1 = 3)

, Brackett series (n1 = 4)


i   
         
 
" 
 
ë Calculate the wavelengths of the first line and
the series limit for Lyman series for hydrogen

è 

$


 


ë avelength (V) - length of one complete wave

ë requency (u) ² Number of waves that pass a


point during a certain time period
ë hertz ( z) = 1/s

ë Amplitude (A) - distance from the origin to the


trough or crest
 

   
V   
 
   
|   


V
   
 -
 
"Ô$
 


º




G
G


G
  

G





   .        
"Ô$
 


º




G
G


G
G






"Ô$
 
ë requencyand wavelength are inversely
proportional

m  Vu
c: speed of light (3.00 108 m/s)
V: wavelength (m, nm, etc.)
u: frequency ( z)
"Ô$
 

ë EX
EX::ind the frequency of a photon with a
wavelength of 434 nm.
nm.
ÑIVEN: RK:
u=? u=c/V
V = 434 nm
= 4.34 10-7 m u = 3.00 108 m/s
4.34 10-7 m
c = 3.00 108 m/s
u %&' '(') *+
ÿ, #
 

ë  (1900)
(1900)
ë bserved - emission of light from hot
objects
ë Concluded - energy is
emitted in small, specific
amounts (quanta)
ÿ, #
 

ë Quantum - minimum amount of energy change

ë Energy can be released (or absorbed) by atoms


only in "packets" of some minimum size.

ë This minimum energy packet is called a 3uantu?


ÿ, #
 
ë The energy (G
(G) of a quantum is related to its
(u) by some constant (h
frequency (u (h):

G = au
ëa is known as "Vlanck's
"Vlanck's constant",
constant", and has a value
of 6.63 x 10-34 ƒoule seconds (ƒs)

energy is always e?itted or absorbed in


ë Glectro?agnetic
(h*uu
whole nu?ber ?ultiples of (h*
ÿ, #
 

ë 
 (1905)

(1905)
ë bserved - photoelectric effect
ÿ, #
 

ë Lightshining on a metallic surface can cause


the surface to e?it electrons

ë or each metal there is a ?ini?u? fre3uency of


e?itted, regardless
light below which no electrons are e?itted,
of the intensity of the light
ÿ, #
 

ë The higher the light's frequency above this


minimum value, the greater the kinetic energy
of the released electron (s)

ë By Planck's results Einstein (1905)


1905) was able to
established the photoelectric effect
ÿ, #
 

ë Einstein assumed that the light was a stream


of tiny energy packets called Vhotons

ë Eachphoton has an energy proportional to its


frequency (G=au)
G=a
ÿ, #
 

ë hen a photon strikes the metal its energy is


transferred to an electron

ëA certain amount of energy is needed to


overcome the attractive force between the
electron and the protons in the atom
ÿ, #
 

ë Thus, if the quanta of light energy absorbed


by the electron are insufficient for the
electron to overcome the attractive forces in
the atom, the electron will not be ejected -
regardless of the intensity of the light.
light.
ÿ, #
 

ë If the quanta of light energy absorbed are


greater than the energy needed for the electron
to overcome the attractive forces of the atom,
then the excess energy becomes kinetic energy
of the released electron.
electron.
ÿ, #
 

ë An important feature of this experiment is that


the electron is emitted from the metal with a
specific kinetic energy (i
(i..e. a specific speed).
speed).
ÿ, #
 
ÿ, #
 

ë 
 (1905)

(1905)
ë Concluded - light has properties of both waves
and particles

ö 


 
 
ë Photon - particle of light that carries a
quantum of energy
ÿ, #
 

ë Theenergy of a photon is proportional to its


frequency.

G  au
E: energy (ƒ, joules)
h: Planck·s constant (6.6262 10-34 ƒ s)
u: frequency ( z)
ÿ, #
 
ë EX
EX:: ind the energy of a red photon with a
frequency of 4.57 1014 z.

ÑIVEN: RK:
E=? E = hu
u = 4.57 1014 z E = (6.6262 10-34 ƒ s)
h = 6.6262 10-34 ƒ s (4.57 1014 z)
-(- '('& .
Calculate the smallest amount of energy (i.e. one
quantum) that an object can absorb from yellow light with
a wavelength of 589 nm.
Energy quantum (G) = hu
So, we need to know the frequency u
u
V= c
u = c/V
u = (3.00 x 108 m/s)/(589 x 10-9 m)
u = 5.09 x 1014 s-1

plugging into Planck's equation:

E = (6.63 x 10-34 ƒs)*( 5.09 x 1014 s-1)


E (1 quanta) = 3.37 x 10-19 ƒ
ááá, Ô
 

   


#
0 Ú 
 

 
ë /
" 
(1924)
ë Electromagnetic radiation considered consist of
particles called photons and at the same time
exhibit wave-
wave-like properties (interference and
diffraction)
wave-particle theory to e-
ë Applied wave-

ë e- exhibit wave properties


Depending on experimental circumstances, EÔ radiation
appears to have either a wavelike or a particle like (photon
character.

Louis de Broglie (1892-1987) who was working on his


Ph.D. degree at the time, made a daring hypothesis:

´If radiant energy could, under appropriate circu?stances behave


as though it were a strea? of particles, then could ?atter, under
appropriate circu?stances, exhibit wave-like properties.µ
e went further and reasoned that since waves
are described by their wavelength

and particles are described by their momentum, p


e can relate these two variables by recalling that

Quantum theory says, !    


ó
"
Relativity says, !    

Equate these two equations  ·  " or  · 


ó ó
 
or ·  or ó·
ó 
The first real experimental proof of this relationship
came from Davisson and Ñermer in 1925, who found
that electrons will diffract and interfere like waves, just like
X-ray photons (light).

or example, an electron with a velocity of 5.97 X 106


m/s (mass of an electron =9.11 X 10-28 g) has a
wavelength of:

ó

So, matter and light are composed of particles that
have wave-like properties.

   


á0Úÿ10áèèuÿ#áÚ##uÚ$

VISIBLE LIÑ T ELECTRNS


", Ô
 

ë *


2
  

ë Impossible to know both the velocity and


position of an electron at the same time
", Ô
 

ë or a relatively large solid object, like a bowling


ball, we can determine its position and velocity at
any given moment with a high degree of
accuracy..
accuracy

ë owever, if an object (like an electron) has


wave--like properties then how can we accurately
wave
define its' position?
", Ô
 

ë erner eisenberg (1901-


1901-1976)
1976) concluded that
due to the dual nature of matter (both particle
and wavelike properties) it is impossible to
simultaneously know both the position and
momentum of an object as small as an electron
electron..

ë Thus, it is not appropriate to imagine the


electrons as moving in well
well--defined circular
orbits about the nucleus.
nucleus.
", Ô
 
ë $ 3
 
!  (1926)
Schrödinger's wave e3uation incorporates both wave-
and particle-like behavior for the electron.

pened a new way of thinking about sub-atomic


particles, leading the area of study known as wave
?echanics, or 3uantu? ?echanics.

Schrödinger's equation results in a series of so


called wave functions, represented by letter Ü (psi
", Ô
 

ë $ 3
 
! 
ë finite # of solutions 8 quantized energy levels
ë defines probability of finding an e-
   G  
ë rom the classical law of energy, the total energy E is the
sum of the kinetic energy K and potential energy V,

K + V=E (1)
# "
The kinetic energy K =  (2)
"
"
Potential energy V = (3)

# "
Total energy E =  " (4)
"

The fundamental equation for wave propagation in any


medium along x²direction at any time  is represented
by a partial differential equation,

}ƒ # }ƒ
" "
(5)
"
· " "
}  }

here ƒ is the displacement of wave velocity , in the


direction of x-axis.
Taking into consideration of ÿ 
  co co--ordinates
x, y and z, the general equation becomes,

}ƒ }ƒ }ƒ # }ƒ
" " " "
(6)
"
 "
 "
· " "
} } }  }
ƒ

here ƒ is a function of time and the exponential


form of the motion of the wave of frequency u is
given by the equation

"i u 
Ü  (7)

here Ü is the amplitude of wave and a function of x, y


and z, but not of time unlike ƒ and  is equal to square
root of -1.
n differentiation twice of the equation (7) with respect to
¶·, we get,
"
} "i u 
"
  $i u Ü 
" " (8)
}

Similarly, on differentiating twice of the equation (7) with


respect to x, y, z co
co--ordinate and adding, we have,

} "ƒ } "ƒ } "ƒ " u   } "Ü } "Ü } "Ü 


"
 "  " ·  "  "  "  (9)
} } }  } } } 
n substituting the identities from equation (6) and (8),

"i u   } "Ü } "Ü } "Ü  # } "


  " " "   " "
 } } }   }

} Ü } Ü } Ü  #
" " "
 "i u 
 " " "   " £ $i "u "Ü  "i u 
 } } }  

"
}Ü }Ü }Ü "
$ u Ü
" " "
(10)
 "
 "  " · "
} } } 
The Schrödinger wave equation, may be written as,

} Ü } Ü } Ü ' 
" " " "

"
 "  "  " £ &% Ü · M (11)
} } } 
hen look at the results obtained from the
Schrödinger wave equation, we talk in terms of
the radial and angular parts of the ave
functions.

aving solved the wave equation, what are the


results?
[ The wave function Ü is a solution of the
Schrödinger equation and describes the
behavior of an electron in region of space
called the atomic orbital.

[ e can find energy values that are associated


with particular wave functions.

[ The quantization of energy level arises, from


the Schrödinger equation.
Energy of the particle in a one dimension box:
Energy of the particle in a one dimension box

 ß   
à     ß 
   ß   aàa    

Thus,
E1 = h2 / 8a2m when n = 1
E2 = 4h2 / 8a2m when n = 2
E3 = 9h2 / 8a2m when n = 3

E4 = 16h2 / 8a2m when n = 4



 
 
 


i 
( 
       
) *   +       
 
  
,  


   ß   G++

G

G&&

G
", Ô
 
ë   (´electron cloudµ)
(´electron
ë Region in space where there is 90% probability of
finding an e-

   u  0 ÿ 

Thus, Schrödinger's equation does not tell us exact location of


electron, rather it describes probability of an electron.
Wave functions and Orbitals

 = wave function
2 = probability density
4 r22 = radial probability function

polar coordinates
0
 
 
" 
 
 

In the Bohr model, the electron is in a defined orbit, in the


Schrödinger model we can speak only of probability
distributions for a given energy level of the electron.

or example, an electron in the ground state in a


ydrogen atom would have a probability distribution
which looks something like this (a more intense color
indicates a greater value for Ü2, a higher probability of
finding the electron in this region, and consequently,
greater electron density):
ÿ. Quantu? Nu?bers

ë è , Ú


1
ë Specify the ´addressµ of each electron in an atom
ÿ, Ú


'  , Ú


45

ë Energy level

ë Size of the orbital

ë n = no. of orbitals in
the energy level
ÿ, Ú


ë corresponds to n from Bohr model

ë describes energy level and size of orbital

ë n = 1, 2, 3, ...

ë as n increases,
ë orbitals get larger
ë orbital energy increases
ÿ. Quantu? Nu?bers

(( l 
 Ô
, 
ë Energy sublevel
ë Shape of the orbital

 

ÿ, Ú


l = Orbital angular ?o?entu? 3uantu?

ë describes shape of orbital

ë l can have integral values from 0 to n-1

ë l values describe a specific shape of orbital:


if l= 0 1 2 3
s p d f
ë The classification of orbitals into subshells and shells
ÿ. Quantu? Nu?bers

ë n = no. of sublevels per level


ë n = no. of orbitals per level
ë Sublevel sets: 's, -p, 6d, 7f
ÿ. Quantu? Nu?bers

-Ô 
, Ú
(
Ú
( ?l 
ë rientation of orbital
ë Specifies
the exact orbital
within each sublevel
ÿ. Quantu? Nu?bers

?l = ?agnetic 3uantu?
ë describes orientation of orbital in space

ë ?l can have integral values from -l to +l


+l
ÿ. Quantu? Nu?bers

  +
ÿ. Quantu? Nu?bers

ë rbitals combine to form a spherical shape.

&
&)
& &%
Quantu? Nu?ber Relationships
Orbital Gnergy ºevels for wydrogen

Õ
   @ 
 
 - 
.
ÿ. Quantu? Nu?bers

Ôulti--Glectron Ato?s
Ôulti

ë Schrödinger equation can be solved only for


hydrogen atom (a one electron system)!

ë or other multi-


multi-electron atoms, assume orbitals
are hydrogen
hydrogen--like.
like.
Orbital Gnergy ºevels in Ôulti-
Ôulti-Glectron Ato?s


  &  
  
     @ 
Õi  

è à a @   
ÿ. Quantu? Nu?bers

Ú
(( ?s 
)$, Ú

ë Electron spin 8 (anti Clockwise, +½ or Clockwise -½)
ë An orbital can hold 2 electrons that spin in opposite
directions.
ÿ. Quantu? Nu?bers

?electron spin 3uantu? nu?ber


electron

?s = +½ or -½
spin-up spin-
spin- spin-down
p
ÿ. Quantu? Nu?bers

u
  
 

[ Aufbau Principle
[ Pauli Exclusion Principle
[ und·s Rule
ÿ. Quantu? Nu?bers

Aufbau Vrinciple
Aufbau is Ñerman for ´building upµ

Electrons enter orbitals of


lowest energy first.
Ñ

u


ë    

ë Electrons fill the


lowest energy
orbitals first.
ë ´Lazy Tenant
Ruleµ
ÿ. Quantu? Nu?bers

Vauli Gxclusion Vrinciple

An atomic orbital may at most


describe two electrons.
ÿ. Quantu? Nu?bers

ë  

ë No two electrons in an atom can have the same 4


quantum numbers.
ë Each e- has a unique ´addressµ:

'  ,Ú x






 Ô,Úx
Ô,Úx 

4888 5
-Ô 
,Ú x   
)$,Ú x

 
Ñ

u

ë  

ë Each orbital can hold # electrons with opposite


spins.
ÿ. Quantu? Nu?bers

* u

hen electrons occupy orbitals of


equal energy,
ë one electron enters each orbital
ë until all the orbitals contain one
electron with parallel spins.
Ñ

u

ë * u

ë ithin a sublevel, place one e- per orbital before


pairing them.
ë N ´Empty Bus Seat Ruleµ

012/ 
/

 ÿ  
Notation for Glectron Distribution

   


   Ú 
 
 

     


  
  Ú  


   
Vrinciple 3uantu? nu?ber ¶n·

The large number "1" refers to the


principle quantum number "n"

 

which stands for the energy level. It tells us that


the electrons of helium occupy the first energy
level of the atom.
Angular ?o?entu? 3uantu? nu?ber I

The letter "s" stands for the angular


momentum quantum number "l"
"l"..

 

     .   


 33    
iotal Nu?ber of Glectrons

The exponent "2" refers to the total number of


electrons in that orbital or sub
sub--shell.
shell.

 

In this case, we know that there are two electrons in


the spherical orbital at the first energy level.
Vrinciple Quantu? Nu?ber (n and Sublevels

ë The number of sublevels that an energy level


can contain is equal to the principle quantum
number of that level.
$


[ The second energy level would have two sublevels,
[ The third energy level would have three sublevels.
[ The first sublevel is called an s sublevel.
[ The second sublevel is called a p sublevel.
[ The third sublevel is called a d sublevel and
[ the fourth sublevel is called an f sublevel.

Although energy levels that are higher than 4 would contain


additional sublevels, these sublevels have not been named because no
known atom in its ground state would have electrons that occupy them
iotal Nu?ber of Orbital and Glectrons per Gnergy ºevel

ë An easy way to calculate the number of orbitals found


in an energy level is to use the formula n2.

ë or example, the third energy level (n=3


(n=3) has a total
of 32
32,, or nine orbitals
orbitals..

ë This makes sense because we know that the third


energy level would have 3 sublevels;
sublevels; an s sublevel
with one orbital, a p sublevel with 3 orbitals and a d
sublevel with 5 orbitals.
orbitals. 1 + 3 + 5 = 9, so the
formula n2 works!
Orbital Gnergy ºevels in Ôulti-
Ôulti-Glectron Ato?s
iwG UºiIÔAiG iOOº
iwG iOOº

ë Remember to start at the beginning of each


arrow, and then follow it all of the way to the
end, filling in the sublevels that it passes
through.. In other words, the order for filling
through
in the sublevels becomes;
becomes;
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f,
5d, 6p, 7s, 5f, 6d,
d,77p.
Ú 

ë   0  

1
*  & &

ë 
 ÿ  

   
Ú 

ë / ÿ  

 * & & &


 & &  
 +

 
  

ë $   ÿ  

* 425 &+



 





  @




 @
†    

@
ááá 
      
   Õ     
   


   
   


   
  



  ! "
# 
  




 
  

  


 

  



ááá 
      


   
( )

$
%
&

'




*
ááá         
 N 
 

 

 
 spdf    

 @) Õ J)

G 

  spdf   
  
   

  

    
  

    
   

    

    
ááá 
      
N  

 
spd   

 @)   J)



    spd 
) )
 «N  
 «N  
«N    
$ «N   

+ «N    

$ «N    

«N    

«N    

 ÿ   


rite ground state electron configurations


(using noble gas notation) for the following:
a) potassium, K (9'&
(9'&)) « à  
b) iodine, I (96-
(96-)) «à    
c) bismuth, Bi (9:-
(9:-)) «a     
So?e Glectron ÿonfiguration Gxceptions

ë Chromium, Cr (Z=24)
expected: [Ar]4s2 3d4
actual: [Ar] 4s1 3d5

ë Copper, Cu (Z=29)
expected: [Ar] 4s2 3d9
actual: [Ar] 4s1 3d10
Why Gxceptions;

ë Recall: energy levels get closer in energy as n


increases.

ë Also, special stability of filled or half-


half-filled
subshells.
$ 
ë 
 ÿ  

ë Copper

EXPECT: [Ar] 4s2 3d9

ACT
ALLY: [Ar] 4s1 3d10

ë Copper gains stability with a full


d-sublevel.
$ 
ë 
 ÿ  

ë Chromium

EXPECT: [Ar] 4s2 3d4

ACT
ALLY: [Ar] 4s1 3d5

ë Chromium gains stability with a half-


half-full d-
d-sublevel.
Glectrons in Subshells - a ÿloser ºook

N (Z=7): 1s2 2s2 2p3

1s 2s 2p
Vara?agnetic vs Dia?agnetic

ë   
 - at least one unpaired electron.

ë 0  
 - all electrons are paired.

ë Paramagnetic species are attracted to a magnetic


field.

ë Diamagnetic species are repelled by a magnetic


field.
Glectron ÿonfigurations for Ions

ë Ôetals lose e- and nonmetals gain e-.

ë rite configuration for parent atom, then add


or remove electrons in outermost shell.

ë ex: e3+
e (Z=26) [Ar]4s2 3d6
e3+ [Ar] 3d5
ÿore Glectrons vs Valence Glectrons

ë core electrons - electrons in inner shells


ë valence electrons - electrons in outer shell

ÿ  «a  
 aa a aà 
 àa a aà 

  a àa      a  aa a aà