two-dimensional (2+n) rempi spectroscopy: state interactions, photofragmentations and energetics of...

TWO-DIMENSIONAL (2+n) REMPI SPECTROSCOPY: STATE INTERACTIONS, PHOTOFRAGMENTATIONS AND ENERGETICS OF THE HYDROGEN HALIDES

 JINGMING LONG, HUASHENG WANG, KRISTJÁN MATTHÍASSON,

HELGI RAFN HRÓÐMARSSON, ÁGÚST KVARAN Science Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, Iceland.

Oral presentation at “international Symposium on Molecular Spectroscopy; 66th Meeting”June 20-24, 2011, Ohio State University

Voltagedevider

HV-2Kv

HX nozzle

TurboPump

TOF

lense

MCP detector

oscilloscope

computer

Excimer Laser

In

out

Dye- Laser

SHG

Time delay200-1200 S

laser control

Pellin Broca prism

SHG control

In

out

REMPI = Resonance Enhanced MultiPhoton Ionization

Resonance Excitation to high energy states of neutral species,followed by photon ionization;For example:

1xh

2xh

2

E

AB

AB+ + e

AB**

-28.5

-28.0

-27.5

-27.0

-26.5

-26.0

x103

4003002001000

Intensity

Mw1 3512

H+

35Cl+

H35Cl+

H37Cl+

12C+

Two photon resonance excitation=82842.36 cm-1

Mass spectrum RCl = HCl

80

70

60

50

40

30x1

03

8006004002000

82849.4 cm-1

j´=2

82848.76j´=3

82847.8j´=4

82846.44j´=5

82844.84j´=6

82836.36j´=9

82842.36j´=7

82839.8j´=8

82833.6cm-1

82842.88

Mw / rel.

35Cl+

H35Cl+

H37Cl+

30,0323

32,1132

34,2637

36,484

38,7739

41,1336

43,5629

46,0619

82

83

3,6

82

83

5,6

7

82

83

8,4

24

82

84

0,7

14

29

82

84

2,3

6

82

84

4,1

27

27

82

84

6,2

4

82

84

7,9

92

82

84

9,8

26

67

82

85

1,7

46

67-30000-28500-27000-25500-24000-22500-21000-19500-18000-16500-15000-13500-12000-10500-9000-7500-6000-4500-3000-15000

150030004500600075009000

10500120001350015000

2xhv

Mw

35Cl+

37Cl+H37Cl+

H35Cl+

/cm-1

r(H-X)

Energy

HX

H X ** H+--X-

      HX+         H+         X+

e-

e-

+

HX REMPI:

IE limit

v´

J´

v´

J´

r(H-X)

Energy

HX

H X ** H+--X-

HX+ H+ X+

e-

HX+ H+ X+

e-

e-

+

HX REMPI:

IE limit

v´

J´

v´

J´

Rel

ativ

e in

ten

sity

/a

.u.

81.45x103

81.4081.3581.3081.2581.2081.15Wavenumber 2h/cm

-1

I1 Q

2468

P

234567

R

2 3 4 5 6 7 8

S

2 3 4 5 6

H79Br+

r(H-X)

Energy

HX

H X ** H+--X-

HX+ H+ X+

e-

HX+ H+ X+

e-

e-

+

HX REMPI:

IE limit

v´

J´

v´

J´

Rel

ativ

e in

ten

sity

/a

.u.

81.45x103

81.4081.3581.3081.2581.2081.15Wavenumber 2h/cm

-1

I1 Q

2468

P

234567

R

2 3 4 5 6 7 8

S

2 3 4 5 6

H79Br+

Re

lati

ve i

nte

ns

ity

/a

.u.

81.45x103

81.4081.3581.3081.2581.20Wavenumber 2h/cm

-1

I1 Q2468

P234567

R2 3 4 5 6 7 8

S2 3 4 5 6

H79Br+

r(H-X)

Energy

HX

H X ** H+--X-

HX+ H+ X+

e-

HX+ H+ X+

e-

e-

+

HX REMPI:

IE limit

v´

J´

v´

J´

Re

lati

ve

in

ten

sit

y

/a.u

.

80.05x103

80.0079.9579.9079.85Wavenumber 2h /cm

-1

Q0123456

V1(m+8)

79Br

+

Br atomicline7

270 cm-1

350x103

300

250

200

150

100

50

Re

lati

ve

in

ten

sit

y

/a.u

.

81.45x10381.4081.3581.3081.2581.2081.15

Wavenumber 2h/cm-1

I1 Q

2468

P234567

R2 3 4 5 6 7 8

S2 3 4 5 6

79Br+

H79Br+

V 1+(v´=m+10)

500x103

400

300

200

100

0

Rel

ati

ve

inte

ns

ity

/a

.u.

80.00x10379.9579.9079.85

Wavenumber 2h /cm-1

Q0123456

V1(m+8)

H79

Br+

79Br

+

Atomic line

7

180x103

160

140

120

100

80

E [

cm-1

]

4321r [Å]

H + Cl*(2P)

H* + Cl

H + Cl+

H+ + Cl

X(HCl+)

2

HCl** 1

F(HCl*)

1 V(H+Cl

-)

1

180x103

160

140

120

100

80

E [

cm-1

]

4321r [Å]

H + Cl*(2P)

H* + Cl

H + Cl+

H+ + Cl

X(HCl+)

2

HCl** 1

F(HCl*)

1 V(H+Cl

-)

1

85.3685.3585.3485.33x10

3

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F12

2h/ cm-1

Inte

nsi

ty

4x106

3

2

1

0

-1

-2

Rel

ativ

e In

ten

sity

86.4x10386.286.085.885.6

Wavenumber 2hv/cm-1

85.9285.9085.8885.86

x103

35Cl+

H35Cl+

Q

QQ 05

0

0

2468

V1

E1 V1

r(H-X)

Energy

HX

H X ** H+--X-

      HX+/HX+  H+     X+

e-

e-

+

HX REMPI:

IE limit

v´

J´

v´

J´

State

Interactions ?

(1) / 0 (2) / 01 2

c101

a

c202= +

b =c1

´0 c2´0-

1 2

c1c2+2 2

= 1

E

WEci

2

4

2

12

12

2

2

E

W 12:

Interaction

strength

(1) / 0 (2) / 01 2

c101

a

c202= +

b =c1

´0 c2´0-

1 2

c1c2+2 2

= 1

E

WEci

2

4

2

12

12

2

2

E

(1) / 0 (2) / 01 2

c101

a

c202= +

b =c1

´0 c2´0-

1 2

c1c2+2 2

= 1

E

WEci

2

4

2

12

12

2

2

E( ) E(J´)E

E

85.3685.3585.3485.33x10

3

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F12

2h/ cm-1

Inte

nsi

ty

87.6x103

87.4

87.2

87.0

86.8

E v

´,J´

/ cm

-1

-120 -100 -80 -60 -40 -20 0 EJ´+1,J´ / cm

-1

V state

v´=13

v´=14

v´=1

F state

J´=8 J´=8

x

EJ´=8 =11.3 cm-1

HCl:

F12

V1

c12 c2

2

122 ,WEci

X ?

85.3685.3585.3485.33x10

3

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F12

2h/ cm-1

Com-press-ion

E x p a n s i o n

Inte

nsi

ty

87.6x103

87.4

87.2

87.0

86.8

E v

´,J´

/ cm

-1

150100500-50-100 dEJ´+1,J´ / cm

-1

V state

v´=14

v´=1

F state

J´=8

J´=7

J´=8

J´=7

F (v´=1)

fig.3c

87.6x103

87.4

87.2

87.0

86.8

E v

´,J´

/ cm

-1

150100500-50-100 dEJ´+1,J´ / cm

-1

V state

v´=14

v´=1

F state

J´=8

J´=7

J´=8

J´=7

F (v´=1)

fig.3c

2/120

201

2

1202

01 )(4

2

1

2

1EEWEEEi

87.6x103

87.4

87.2

87.0

86.8

E v

´,J´

/ cm

-1

-120 -100 -80 -60 -40 -20 0 EJ´+1,J´ / cm

-1

V state

v´=13

v´=14

v´=1

F state

J´=8 J´=8

x

EJ´=8 =11.3 cm-1

HCl:

F12

V1

c12 c2 = 0.42

122 ,WEci

X ?6 cm-1

from line shifts

r(H-X)

Energy

HX

H X ** H+--X-

      HX+/HX+  H+     X+e-

e-

+

HX REMPI:

IE limit

v´

J´

v´

J´c1

2 c22

? X+

r(H-X)

Energy

HX

H X ** H+--X-

      HX+/HX+  H+     X+e-

e-

+

HX REMPI:

v´

J´

v´

J´

H   +   X

X+

r(H-X)

Energy

HX

H X ** H+--X-

      HX+/HX+  H+     X+e-

e-

+

HX REMPI:

v´

J´

v´

J´

HX*** H    +   X*

X+

r(H-X)

E

HX

H+--X-

      HX+/HX+  H+     X+e- HX REMPI:

v´

J´

v´

J´c1

2 c22

X+

X

X*

c1 c2+2 2

I (HX+) =

c1 c2+2 2

I (X+) =

Ry: I.P./V:

)1(

)1(

)(

)(22

22

c

c

HXI

XI

c22

c22

= X+)/X+)= X+) /X+)= X+)/X+)

r(H-X)

E

HX

H+--X-

      HX+/HX+  H+     X+e- HX REMPI:

v´

J´

v´

J´c1

2 c22

X+

X

X*

)1(

)1(

)(

)(22

22

c

c

HXI

XI

c22

c22

= X+)/X+)

= X+)/X+)

Exp.Q

i=35 i=37

I(i C

l+)/

I(H

i Cl+

)

Exp.Q

Calc. V,v´ = 20

Calc. V,v´=20

j3-1; ´=0

isotopomers H35Cl H37ClJ´ closest resonances(J´res) 2 2|E(J´res) | / cm-1 20.6 14.7W12(J´res) / cm-1 6.5 5.8c1

2 (c22) (J´res) 0.89(0.11) 0.81(0.19)

3.5 4.2 14 x 10-3 13 x 10-3

HiCl j 3-1

>

><

K. Matthíasson et al.J. Chem. Physics,134, 164302, (2011)

r(H-X)

Energy

HX

HX**

H+--X-

      HX+/HX+  H+     X+e- HX REMPI:

v´

J´

v´

J´

H   +   X

X+

j 3-1

t 3+1 S/O

-0.005

0.005

0.015

0.025

0.035

0.045

0.055

2 3 4 5 6 7

J'

-0.005

0.005

0.015

0.025

0.035

0.045

0.055

2 3 4 5 6 7 8

J'

H35Cl f 32 f 31

I(35

Cl+

)/I(

H35

Cl+

)

States f32 f31

J´ closest resonances(J´res) 5 6|E(J´res) | / cm-1 17.7 27.9W12

max(J´res)/ cm-1 2 4c1

2(J´res) 0.987 0.979 4.0 0.5 0 1.0 x 10-3

<

>

Exp.Q

Calc.V,v´=9

Exp.S

Calc.V,v´=8

<

-0.005

0.005

0.015

0.025

0.035

0.045

0.055

2 3 4 5 6 7

J'

-0.005

0.005

0.015

0.025

0.035

0.045

0.055

2 3 4 5 6 7 8

J'

H35Cl f 32 f 31

I(35

Cl+

)/I(

H35

Cl+

)

Exp.Q

Calc.V,v´=9

Exp.S

Calc.V,v´=8

No dissociation

No predissociation pathway

Dissociation:

Predissociation by S/Ocouplings via “Gateway Rydberg states (1,3)”:

H37Cl j 3- (0+)

Exp. Q

89.8

89.6

89.4

89.2

x103

J´=0

J´=6

J´=6 v´=21

J´=6 v´=20

J´=0

J´=0

:

:

j 3- (0+), v´=0

V 1(0+)

H37Cl

Near resonance

S´=0 ´=0

E/c

m-1

Calc. V,v´=20 V,v´=21

H37Cl j 3- (0+)

Exp. Q

V´ states v´=20 v´=21J´ closest resonances(J´res) 6|E(J´res) | / cm-1 65W12

(J´res) / cm-1 25 25c1

2(J´res) 0.82 4.0(52 x 10-3) 4.0(52 x 10-3)

Rel

ativ

e In

ten

sity

77.98x103

77.9677.9477.9277.9077.8877.86

Wavenumber 2hv/cm-1

Q

02489 7 6

E1

79Br

H79

Br

10

H79Br

79.8

79.6

79.4

79.2

x103

J´=0

J´=6

J´=9J´=6 v´=m+5

H79Br

E 1(0+), v´=0

J´=9 v´=m+4

J´=0

V 1(0+)

Off resonance

S S´=0 ´=0

J´=6

J´=0

E/c

m-1

H79Br, E(v´=0)

I(79Br+)/I(H79Br+) Linewidth/cm-1

::Victor Huasheng Wang

Kristján MatthíassonJingming Long

Helgi Rafn Hróðmarsson

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