Ionization: NH or N H + N H +: - Absorption NH

2
-ionization AB+* + e
AB+ + e
1h
Energy
-absorption 
n h n h AB*

or 
n1 h1+
n2 h2 +
: AB
•Why multiphoton exitations(?); advantages/disadvantages
•One color experiments / data
•Experimental methods: Multiphoton ionization (MPI & REMPI)
•Data interpretations / theory: “What to see and what not to see(?)”
•Results / examples:
- characterization of state properties / energies
- (2+1) vs (3+1) REMPI
- ”New” states observed
- analysis of complicated spectra
- state interactions
- multi-photon absorption “mechanism”
- energy distribution in molecules
- polyatomic molecules
•Two color experiments / data
- (2+1) vs (3+1) REMPI
2
Few- photon absorption in atoms and molecules:

Excitation to high energy states of neutral species:
A+ AB+ + e
A** AB**
1xh
2xh
3xh
nxh
A AB
3
1xh 2xh 3xh nxh
Typically: VUV UV Visible Visible..IR
Technically more feasable to increase n
+
4
A+ AB+ + e
A** AB**
1xh
2xh
3xh
nxh
A AB
•Increasing probability of resonance intermediate states.

Hence spectra complications
-
5
Spectroscopic characteristics:
I. Angular momentum quantum numbers (L) can change as:
L = (0),.. n for nxh
Thus electronic angular momentum changes in atoms as
L = 0,1 / l = 1 per “photon step”
1x 3x
6
II. Electronic angular momentum changes in molecules:

z
L  (  1) 
´=3() ´=2() ´=1() ´=0()
3xh 2xh
3xh
1xh i 
2xh
3xh
´´=0()
7
III. Total angular LJ

momentum changes:
LN
J = 0 ,1,.. ,n z
For nxh
L
J-3;N J-2;O J-1;P J:Q J+1;R J+2;S J+3;T
I, II, III =>

More states
can be excited
as n increases
J
8
As n (in nxh) increases:

•Technically feasable +
•Larger number of excited states accessable.
Hence more spectroscopic information +
•Better consistancy / accuracy in determining
spectroscopic parameters due to larger +
number of transitions
•More complicated spectra / more overlap of features -
How to proceed?:
- (2+1) vs (3+1) REMPI
9
I. Experimentally:
a) Simply and inexpensively / for gas samples:
AB+ + e
+
AB**
-
LASER beam
3 photon absorption; 1 photon ionization

i.e.: (3+1)REMPI-Current AB
REMPI-TOF
REMPI
LASERS
TOF
Excimer Laser Pellin Broca prism
SHG
Dye Laser
Out
Time
SHG Control Box
Delay
In 200-1200 S
Nozzle
HX +HV
Dye laser Control
Focus lens
One Shot
External
Cycle
Input TOF Tube

Output
G-Valve
Turbo
Pump
Oscilloscope
MCP Detector
HV
Computer Voltage
EXT
divider -2Kv
supply
REMPI-TOF:
-15
Mass1.2.03;
spectrum of HCl, showing:
Mass spectrum
H+,35according
Cl+,H35to Cl+,37Cl+,H37Cl+ Mw=38(H Cl)
37
Mw=((0.04*n-0.11748)/2.2816)**2
For = 477.795 nm LASER 37
radiation Mw=37( Cl)
35
Mw=1 (H) Mw=36(H Cl)
-20
35
Mw=35( Cl)
3
x10
-25
Mw=12 (C) Mw=28 (N2)
-30
0 10 20 30 40
Mw (amu)
Mass spectra
vs LASER radiation: + +
Cl ,HCl
+ LASER
H
Radiation
frequency
-1
20932 cm
ions
Magn jóna
-1
20931 cm
Number of
-1
20930 cm
LASER
Radiation
-1 wavenumbers
20929 cm
-1
20928 cm
TOF/ion
Flugtími jónamass
/ massi jóna
100
Ion formations
80
vs
LASER radiations 20930.0 cmcm-1-1
83720
37 +
60 H Cl
37 +
Cl
40
3
x10
20
20929.5 cmcm-1-1
83718
35
H Cl
+
35 +
0 Cl
-20
mass
335 340 345 350 355 360
35 n (pnt) 37
Ion formations
20 H
+ vs
LASER radiations
10
REMPI-
TOF (H+)
spectrum
intensity
0
3
x10
-10
20930 cm-1
-20
20929 cm-1
-30
0 1 20 40 60 mass 80 100 120

..AND 35 +
37 + Cl og
REMPI – Cl og
37 + 35 +
H Cl
H Cl
Current
spectrum:
Magn Cl-haldandi jóna
37 +
Cl og
Intensity
37 +
H Cl 35 +
Cl og
35 +
H Cl
3
20.929 20.930 20.931 20.932x10
Bylgjutalawavenumbers
LASER (1/) LASER geisla
(1/ (cm-1))
+ 35 +
37
Cl og Cl og
35 +
37 +
H Cl H Cl
Magn Cl-haldandi jóna

37 +
Cl og
37 +
H Cl 35 +
Cl og
35 +
H Cl
HCl
3
20.929 20.930 20.931 20.932x10
Bylgjutala (1/) LASER geisla
REMPI-Current
Spectrum
Intensity
20850 20900 20950 /cm-1 21000 21050

•Data interpretations/theory: “What to see and what not to see(?)”
- (2+1) vs (3+1) REMPI
11
Interpretation / Theory:
Ej
nxh
n
Determine:
1) Signal intensity  transition probabilities

 population in ground state
E = Ej-Ei = photon energy x n Ei
1xh - absorption:
A/Ifl
 
Exp.
Eh E10
1xh

Calc.
2 
  1 ME 0
E10 E20 E30
Eh=E10=E1-E0
=(E1-E0)/h
A+ AB+ + e

A** : AB**
|i4>
2xh |i3>
 |i2>
2
1 ME i i ME 0
 
i    |i1>
i ,0
=(E1-E0)/h
A AB
AB+ + e

: AB**
|i4>
3xh |i3>
|i2>

2
1 M E i 2 i 2 M E i1 i1 M E 0
   |i1>
i1,i 2 i 2 , 0    i1, 0  2 
=(E1-E0)/h
AB
Approximations:
1) B-O approximation, 2) No resonance intermediate states,
AB+ + e
AB**
1) 2)
2 1 ME i i ME 0
2
|i3>
  1 ME 0  
i  i ,0  |i2>
:
:
:
  cv  e2 s J   e2 s J |i1>
 i 2, 0

rot. contribution  i1, 0
electr. Contrib.
vibr. Contrib. ; cv = fasti
AB
....approximations:
...3) assume virtual intermediate states:
1,2,3), hence:
3)
2
   1 ME 0 .........................    2 s
1 1
2
1 ME i i ME 0
“i”          2
s   2
i i,0 ............. 0 0 2 s2
3xh
“i”
2
1 M E i 2 i 2 M E i1 i1 M E 0
   i 2 , 0    i1, 0  2 
2 2
 i1,i 2 ...   1 1s   3 s3
-for si(J,), i2 = e2

13
2xh
1xh 3xh
  s  s 2
0 0 2
2
  s 2
1 1   12 s1   32 s3
  f ( ,  )
n

   ME  ;     1 ME 
  

 
i2´s are treated as variables in simulation procedures

  12 s1   12 s1   32 s3
s1,s3 J and  dependent;
s1,s3 fyrir ´´= 0:
 = 0 ,1,.. ,n; n = 1,2,3,..

Selection rules: J = 0 ,1,.. ,n; n = 1,2,3,..;   0
J = 0 ,2,.. ,n; n = even  = 0
J = 1,.. ,n; n = odd;  = 0
14
15
1)  Intensity
2) Ei(B,D,0) E (nxh)
Intensity vs (nxh) / I() can be evaluated

and compared with REMPI spectra:
Spectra simulations
- (2+1) vs (3+1) REMPI

Ionization: NH or N H + N H +: - Absorption NH

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Ionization: NH or N H + N H +: - Absorption NH

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2

Few- photon absorption in atoms and molecules:

1xh 2xh 3xh nxh

Typically: VUV UV Visible Visible..IR

Technically more feasable to increase n

•Increasing probability of resonance intermediate states.

II. Electronic angular momentum changes in molecules:

´=3() ´=2() ´=1() ´=0()

III. Total angular LJ

I, II, III =>

As n (in nxh) increases:

3 photon absorption; 1 photon ionization

Input TOF Tube

Mw=12 (C) Mw=28 (N2)

0 1 20 40 60 mass 80 100 120

Magn Cl-haldandi jóna

20850 20900 20950 /cm-1 21000 21050

1) Signal intensity  transition probabilities

1) B-O approximation, 2) No resonance intermediate states,

-for si(J,), i2 = e2

i2´s are treated as variables in simulation procedures

 = 0 ,1,.. ,n; n = 1,2,3,..

Intensity vs (nxh) / I() can be evaluated

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