You are on page 1of 8

c

http://www.chem.qmul.ac.uk/surfaces/scc/scat5_4.htm
5.4 Vibrational Spectroscopy c
c
 
c
 c  c  c   c   c c   c  c  c
 c
   c
c c 
cc c
 c   c c  c   cc
 
 c
 c  cc c  c ccc ccc c  cc c
 c 
 c
c c  c c  c 

 c c  c  c c  c c c c   c  c c  c c


  c  c  c  c
  c   
c c  c  c  c c   c c
  c c !"c  cc

#  c  c   c  c c   c c  c   c  c c c  c c
  cc  cc c c$cc

%c IR Spectroscopy (of various forms, e.g. RAIRS, MIR)cc


&c lectron nergy Loss Spectroscopy ( LS )cc

cc

IR Spectroscopy

#  c  c c  c c  c c  c  c c   c  c  c 


   c c  c  c c
  cc  cc

!c c 
 c
 ccc  c c$cc

#  cc
 
c$c 
 c c  c   c '
 c   c cc c
c c 
 cc  c# c  c c c c  cc 

 c c   c  c


 c  c   c  c c
 ccc  cc  c
 cc c 
 c
# c c 
 c cc  c cc
 c cc

  c  c cc

( c   cc


 
cc(!# cc$cc c c  c   ccc
cc 
 c c   c   cc c# c cc cc  c c c

 c c c  c  c   c 
 c c  c c    c 
 c c  c
 cc  cc

!c  ccc  c c 


 c c  c   c$cc

  ) 
c c
 
c c ) c c $c   c  c c  c  c
 c    c
c cc ccc    c 
 c  c cc c  c  c  c

*
 c c   c
 
cc*c c$c c c cc  c  c
 ccc
c c  c 
 c c c  c  c c c    c   c c  c
  c c  c c c  c  c c  c 
 c )c  c   c  c c  c c
c c c  c c
 c  cc c c  cc  c c  c c
c)  c#c  c)#cc

cc
RAIRS - the Study of Adsorbates on Metallic Surfaces by Reflection IR Spectroscopycc

c c c c    cc c c   ccc     cc  c  c c
 c cc+   c  cc cccc

!  c  c c  cc


 c
c,
cc  c c  c c  c c  c
 cc c  ccc c# c  c cc   c  
 ccc

!c   c cc-c cc ccc


!c  c  c c c  c   cc 
 c 
 c c
+c
  cc

. c/c
 c ccc   c c c c c  c  c -ccc c c
 c c  c   c #
  c  c 
 c  c  c c %c &c c  c c %0%1c
  c   c  c c %c  c 2c  c !#c
   c   c  c
c  c 00%3c c &3c  
c c c  c   c c   c c  c  c %c
%ccc

!c c  c c


  c    c c    c  c c 4c 500c %c c  c c    c
  cc c  ccc cc  c
  cc c ccc c   c
cc c c  c   cc c  c cc c  c
 cc
 c c500cc6500c %cc

Selection Rulescc

# c  c c c  c c   c c   c   c  c / c c  c
surface dipole selection rulecc

# c  c c  c  c c  c  c  c  c c c  c 
 c


 c c c  c  c  c c   c c  c  c c c   c  
c
cc
c

! ccc c  c cc  cc


 
c c ccc c  c
 c 

c7c-   c8)

c
c69c:;%c%<9:=cc c  cc c    cc  c
cc c c cc c c c  c -cc c c c c cc

 amples of Reflection IR Spectracc

%cc> c' c>.c &cc@A>c 


ccc?c
 
ccc?c  cc  c

c c

cc

lectron nergy Loss Spectroscopy (LS)

# c cc  c c c   c  ccc   c   cc cc   c
c
cc  c
 c$c 
  cc c c    c c c   c
cc
 
cc

#cc  cc c  c   c c  cc c   c   cc cc

@ ccc c cccorccc  ccc cc

 c  c   c 
 c c   c   c c  c   c    c c  c c c
 c@ ccB@ c   cc  c c cc  cc   c   c   c
cc cc  c
 c  cc cc c cc  cc  cc
 c  cc c  cc  c  c   cc

# c  c '
 c   c c c 
 c c  c    c ccc c
 c c  c  cc  c c    c  c c   c c c ' c   c
  cc c c c   c   c cc


 c  c   c cc
c

)c  c cc   c c    c   cccCcccc c c ccc c
elastic peakcc c
cc

.c  c c -  c   c  c c  c c


-c c c 4c c c c  -c
- c  c


 ccc c 
c -c# c
- c 
cc   c c c
  c   c   c cc c  cc c  cc

# c  c c  c   c  c Dc Cc c c c  c c c c c c  c  c
  c c  c c  c c  c   c '  c c  c    c  c
 c c

  c c  c   cccc c  cc c c1%0c cc   c
cc
&00c cc cc c c
 c c c   c c   c   cc cc

Selection Rulescc

# c  c cc   c  cccc c c  c


c
c c
 cc c   cc c c '
 c   $c
  c c cc c  c
c c   c  cc
cc c  cc

½or metallic substratesccc


c   c  c c
 
 c cc c
 c
  ccc c  c c c  c c   c  cc c c cc
 ccc
 c  ccc c  c c c  cc

E c  ccc
c   c   c c   cc  c
 c cc 
 c
 c  c  ccc c  c c c  c c   c -ccc
 c c cc c c  cc

c
c c c  ccRothc
cc
c c c  c cc  c
  c c c
ccc cc 
c c ccc c  c
  cc c cc   cc c  c
 cc
# c cc c  c
 c c@ c  cFc c   c c
cGc:090c
%c cc
 c)c   cc c  c c c c c-cc c!2@*c
ccc'cc c   c
-cc

# c
c c c  c
  cc  c  c   c c  c

 cc  c c
   cc  c c
 c
c c
  cc
 c  c
c cc4c%0c %cccc  c  c c cc c
  cc

c  c  c cc cc  cc c c c

 ccc
  cc c  cc  c
 cc  c c cccc

!c c   cc
!c  c  c cc
!c
c  cc c:00c %cc

c   cc c cccc

!c  ccc   c   c cc@ c  cc  c c ccc


 
 cc  c - c
 cc c c cc  c  cc
  c c  c cc c cc c 
 cc
!c    ccc
   c  c   cc
!c  c cc

cc

Applications of Vibrational Spectroscopy

. c c  c   c '
 c c c  c c  c c
 
c  c  c
  cc c  cc c  c    ccc  c ccc$cc

Golecular Adsorption of CO on Getallic Surfaces


)  c c' c  c c cc c 
 ccc ccc c

cc cA.c   c   c# c  c   c c c:00c %cc c
  c c  cc cc

# c 
 cc
ccA.c cc  c  c
 c c  c
cc
c
c   c  c   c c c 
 ' c c  c   c c  c 
 ' c
  c c cc' c  c  c c     cc

# c 
 c   cc cA.c   c   c c
 ccc cc c
 c cc c  c$c ccc  cc

cc HA.c
A.cc c
 cc &%:6c %c
# cA.c &%00cc%<&0c % c
Ecc&c  cc %<&0cc%900c % c
Ecc6c,c:c  cc 4c%900c %c

 amplec$cc

ccc)c
ccA.c    ccc  c?c  cc

# c  cc c   c   cc  cA.cc c c  cc


 c c
 c  cc&%:6c %cc c c '
 cc  cc c( AccBlyholder
modelcc cccA.cc  cc

# c 
 c c    c c A.ccc   cc
cc 
  c$cc

Ac$c c ccIc  c cc 


ccc cc
J c
Jccc c ccc 
 c c cc
 c  c   cc c  cc  c   c  cc
 cA.c  cc c c  cc

c$c c ccKcc  c cc 


cc c cKc
c
KcLc cc cKMcc ccc c
A.c  c  c c  c  cc c cc
 c   cc cA.ccc  c cc
  c  cc cA.cc  cc c  c
c   c  cc c  c  cc

c
!cc c  c   cc cccA.cc  c c c   cc  c
c cc cc$c
Jc) c cA   cJc c!)cAc7c"c2- c1cc

c19cc5&cc
Jc  c7c  c$cc   N c cccc '  c   cJc cc@c

c;%
;:cc