Quantum

 Chemistry  

Lecturer:  Aulia  Sukma  Hutama  

Laboratory  of  Physical  Chemistry,  Department  of  Chemistry,  
Universitas  Gadjah  Mada  
aulia.sukma.hutama@ugm.ac.id  
 Timeline  

(7  weeks)  
 
1.  IntroducNon  to  Quantum  Mechanics  
2.  SoluNon  of  Schroedinger  EquaNon  I  
3.  SoluNon  of  Schroedinger  EquaNon  II    
4.  Hydrogen(ic)  Atom    
5.  Many  electron  Atom  
6.  Molecular  structure  I    
7.  Molecular  structure  II  
 
(Exam)  
 
References:    
 P.  Atkins,  Molecular  Quantum  Mechanics  
I.  Levine,  Quantum  Chemistry    
 EvaluaNon  

Mid  Exam  :  40  %  

Homework  :  10  %  

Exam:  to  be  determined  

I  would  not  count  your  aZendance,  however  the  

Department  requires  at  least  80  %  of  your  aZendance  to  
pass  this  class.  
IntroducNon  to  Quantum  Mechanics  
 Why  Quantum  Chemistry?  

There  are  many  studies  in  the  field  of  chemistry  

Examples:  

Chemical  reacNon   Molecular  spectroscopy  

What  is  the  role  of  quantum  chemistry?  

 Chemical  ReacNon  

Explaining  the  reacNon  mechanism     May  be  explained  from  

chemical  bonding  and  orbitals  
Example:  catalyNc  reacNon  

Concept  in  quantum  chemistry  

L.  Lv.  et  al.,  Organometallics,  32,  3837  (2013).      
Involving  many  elementary  process  
 Spectroscopy  

In  toluene  

R.A.  Alder  et  al.,  Inorg.  Chem.,  56,  8718  (2017).      

Fluorescence  is  greatly  affected  by  the  structure  and  solvent.  Why?  By  employing  
quantum  chemical  methods  we  can  answer  the  quesNons.    

In  the  end,  experimentalists  are  helped  by  the  insight  from  quantum  chemistry  knowledge    
 Quantum  chemistry:  where  to  start?    

Universe  visible  to  us  is  usually  called  macroscopic  universe.  

The  laws  governing  macroscopic  universe  is  the  classical  

(  Newtonian)  mechanics.  

“Unfortunately”  the  microscopic  universe  has  totally  different  

physical  laws.  The  laws  governing  microscopic  level  is  called  
quantum  mechanics  

We  will  see  later  at  what  condiNon  at  we  have  to  use  quantum  mechanics  
 Classical  Mechanics  
v  

m  

0   x  

Quiz  :    
 
1.  Other  than  the  wriZen  above,  what  physical  quanNNes  does  
that  body  have?  
2.  Suppose  that  you  track  the  movement  of  above  body  in  t  
(4me).  Express  the  posiNon  at  t!  
3.  How  many  possibility  of  (kineNc)  energy  value  does  above  
system  have?  Suppose  the  velocity  varies  from  v0  to  vmax  
 Classical  Mechanics  
v  

m  

0   x  

Answers  :    
 
1.  Momentum  and  kineNc  energy  
2.  x  =  vt  
3.  There  are  infinity  possibility  of  kineNc  energy  value  between  v0  
to  vmax    
 Classical  Mechanics  

•  Predict  posiNon  (and  momentum)  precisely.  (Answer  

2)  
•  Allow  conNnuous  energy  and  generally  observable  
quanNty.  (Answer  3)  
         
Classical  moNon  

TranslaNon   RotaNon   VibraNon  

Black-­‐body  RadiaNon  

OZo  Lummer  experiment  ca.  1890  

Hoffmann,  2000,  Physikalische  BläZer  56,  43  

•  A  hot  object  emits  radiaNon  

•  Perfect  absorber  =  Perfect  emiZer    
Black-­‐body  RadiaNon  

Experimental  results  

dE
5000  K  
=ρ
dλ

4000  K  

3000  K  

0 500 1000 1500 2000

(nm)
Black-­‐body  RadiaNon  

Rayleigh-­‐Jeans’  Law  
Derived  from  classical  
mechanics  and  
5000  K  
thermodynamics  
8π kT
4000  K  
ρ= 4
λ
3000  K  

0 500 1000 1500 2000

(nm)

Ultraviolet  catastrophe  !!  

Black-­‐body  RadiaNon  

Max  Planck  came  with  ideas  

Planck’s  Law  
•  EM  waves  are  
considered  as  
5000  K   oscillator  
•  E  =  nhν with  n  =  0,  
1,  2,  …  
4000  K  
8π hc exp(− hc λ kT )
ρ= 5
3000  K   λ 1− exp(− hc )
λ kT
0 500 1000 1500 2000
(nm)

Reproduces  the  experimental  curves  !!  

Heat  capacity  

•  Dulong  and  PeNt  discovered  that  the  heat  capacity  of  any  solid  is  
approximately  25  J/mol  K  

•  The  mean  energy  of  atom  in  solid  as  it  oscillates  about  its  original  
posiNon  is  kT.  For  3  degree  of  freedom,  the  energy  is  3kT.  Thus,  for  
NA  atoms,  the  total  energy  becomes  

U = 3N A kT = 3RT
•  From  the  definiNon  of  heat  capacity  
dU
CV = = 3R
dT
•  Agrees  with  Dulong  and  PeNt  experiment  
Heat  capacity  

•  From  experimental  results,  the  heat  capacity  tended  towards  to  zero  as  
T  à  0  
•  Einstein  implemented  the  idea  of  Planck  that  the  atom  can  be  
considered  as  oscillator  with  single  frequency    
4

3.5 Dulong-­‐PeNt  value  

3

2.5 θ 2 exp(θ T )
CV = 3R( )
T (1− exp(θ ))2
Cv/R

1.5
T
1

0.5

0
0 0.5 1 1.5 2 2.5 3
T/

•  This  is  not  the  best  approximaNon,  but  the  discussion  are  going  to  the  
right  direcNon  
Photoelectric  effect  

Discovered  by  Hertz    

Ek = hv − φ

h
Proof  that  light  has  momentum     p=
λ
Compton  scaZering  

Due  to  conservaNon  of  kineNc  energy  and  momentum,  the  scaZered  
photon  has  longer  wavelength    

h Where  does  the  momentum  come  from  ?  

λ f − λi = (1− cosθ )
mec
Atomic  Hydrogen  Spectra  

Balmer  empirical  
formula  
" n2 %
λ = 364.506 $ 2 '
#n − 4&

GeneralizaNon  by  
Rydberg  

1 "1 1 %
= RH $ 2 − 2 '
λ #n m &

SNll  no  theoreNcal  explanaNon  

The  Duality  of  MaZer  

de  Broglie  relaNon    

h
λ=
p

Experimentally  proven  by  

Davison-­‐Germer  (1927)    

Proof  that  electron  has  wave  property  

FoundaNon  of  Quantum  Mechanics  

1.  The  state  of  a  system  is  fully  described  by  a  funcNon  Ψ(r1,  
r2,  .  .  .  ,  t).  
•  Recall  de  Broglie  hypothesis  
•   The  funcNon  contains  any  informaNon  about  the  parNcle(s)  
 
2.  The  wavefuncNon  must  be  conNnuous,  differenNable,  and  
having  finite  value  
3.  The  probability  that  a  parNcle  will  be  found  in  the  volume  
element  dt  at  the  point  r  is  proporNonal  to  |Ψ(r)|dt.  
FoundaNon  of  Quantum  Mechanics  

4.  Every  observables  have  mathemaNcal  representaNon  

•  These  are  the  most  important  operator  
 
  !∂
px ⇒ p̂x ≡ x ⇒ x̂ ≡ x ×
  i x
 
5.   The  form  of  Nme  dependent  Schrödinger  equaNon  
  Ĥ Ψ = EΨ
 
(T̂ + V̂ )Ψ = EΨ
 
! d 2Ψ
  − 2
+V Ψ = EΨ
2m dx

6.  It  is  impossible  to  “measure”  momentum  and  posiNon  

simultaneously  with  accurate  precision   Δpx Δx ≥ !
1
    2
 Homework  
•  Find  the  applicaNon  of  the  wave  characterisNc  
of  electron  in  chemistry.  

•  Reading  assignment:  
–  Matrix  
–  Second  order  differenNal  equaNon  
–  Eigenvalues  and  eigenfuncNons