ÁGÚST KVARAN, et al.

PHOTOFRAGMENTATIONS, STATE INTERACTIONS AND ENERGETICS OF HALOGEN CONTAINING MOLECULES: TWO-DIMENSIONAL (2+n) REMPI

ÁGÚST KVARAN, et al. Science Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, Iceland.

Oral presentation at PSI / SLS, June, 2012.

Voltagedevider

HV-2Kv

RX 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

1xh

2xh

2

E

AB

AB+ + e

AB**(2 + 1) REMPI


1xh

2xh

2

E

AB

AB+ + e

AB**

A + B+ + e


1xh

2xh

2

E

AB

AB+ + e

AB**

A + B+ + e

AB # #

AB+ + e

A+ + B + e

A + B+ + e

A + B/B*


1xh

2xh

2

E

AB

AB+ + e

AB**

A + B+ + e

AB # #

AB+ + e

A+ + B + e

A + B+ + e

A+ + e

B+ + e

(2 + n)REMPI; n = 1,2,.....

.....A+..............B+..........................AB+..... / Mw

I(M+)

Laser excitation / cm-1

2D - REMPI

• PHOTOFRAGMENTATIONS, • STATE INTERACTIONS • ENERGETICS

I. Small molecules:Diatomic moleculesLinear molecules

II. “Bigger molecules”Polyatomic molecules

Data:Rotational (J) structureresolution

Data: Vibrational (v) structureresolution

Analysis (J-dependent):•Signal Intensities•Power dependences•Line-shifts•Line-widths

Analysis (v-dependent):• Signal intensities• Power dependences

Results (J-dependent): • Energetics• n,(2+n)• State interactions• Photofragmention• Lifetimes

Results (v-dependent): •Energetics• n,(2+n)• State interactions• Photofragmention

-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+

30,032332,113234,2637

36,484

38,7739

41,1336

43,5629

46,0619

8283

3,6

8283

5,67

8283

8,42

4

8284

0,71

429

8284

2,36

8284

4,12

727

8284

6,24

8284

7,99

2

8284

9,82

667

8285

1,74

667-30000-28500-27000-25500-24000-22500-21000-19500-18000-16500-15000-13500-12000-10500-9000-7500-6000-4500-3000-15000

15003000450060007500900010500120001350015000

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

tens

ity /

a.u.

81.45x10381.4081.3581.3081.2581.2081.15Wavenumber 2h/cm-1

I1 Q

2468

P234567

R

2 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´

Rel

ativ

e in

tens

ity /

a.u.

81.45x10381.4081.3581.3081.2581.2081.15Wavenumber 2h/cm-1

I1 Q

2468

P234567

R

2 3 4 5 6 7 8

S2 3 4 5 6

H79Br+

Rel

ativ

e in

tens

ity /

a.u.

81.45x10381.4081.3581.3081.2581.20Wavenumber 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´

Rel

ativ

e in

tens

ity /

a.u.

80.05x10380.0079.9579.9079.85Wavenumber 2h /cm-1

Q0123456

V1(m+8)

79Br+

Br atomicline7

270 cm-1

350x103

300

250

200

150

100

50

Rel

ativ

e in

tens

ity /

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

ativ

e in

tens

ity /

a.u.

80.00x10379.9579.9079.85Wavenumber 2h /cm

-1

Q0123456

V1(m+8)

H79Br+

79Br+

Atomic line

7

180x103

160

140

120

100

80

E [c

m-1

]

4321 r [Å]

H + Cl*(2P)H* + Cl

H + Cl+

H+ + ClX(HCl+)2

HCl** 1

F(HCl*)1 V(H+Cl-)1

180x103

160

140

120

100

80

E [c

m-1

]

4321 r [Å]

H + Cl*(2P)H* + Cl

H + Cl+

H+ + ClX(HCl+)2

HCl** 1

F(HCl*)1 V(H+Cl-)1

85.3685.3585.3485.33x103

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F12

2h/ cm-1

Inte

nsity

4x106

3

2

1

0

-1

-2

Rel

ativ

e In

tens

ity

86.4x10386.286.085.885.6Wavenumber 2hv/cm-1

85.9285.9085.8885.86x10

3

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

c101a c20

2= +

b =c1´0 c2

´0-1 2

c1c2+2 2 = 1

E

WEci

2

4

21

212

2

2

E

W 12:

Interaction

strength

(1) / 0 (2) / 01 2

c101a c20

2= +

b =c1´0 c2

´0-1 2

c1c2+2 2 = 1

E

WEci

2

4

21

212

2

2

E

(1) / 0 (2) / 01 2

c101a c20

2= +

b =c1´0 c2

´0-1 2

c1c2+2 2 = 1

E

WEci

2

4

21

212

2

2

E( ) E(J´)E

E

85.3685.3585.3485.33x103

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F12

2h/ cm-1

Inte

nsity

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 ?

85.3685.3585.3485.33x103

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

nsity

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

2/1202

01

212

02

01 )(4

21

21 EEWEEEi

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´

c12 c2

2

? 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´

c12 c2

2

X+

X

X*

c1 c2+2 2I (HX+) =

c1 c2+2 2I (X+) =

Ry: I.P./V:

)1()1(

)()(

22

22

cc

HXIXI

c22

c22

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

r(H-X)

E

HX

H+--X-


v´J´

v´J´

c12 c2

2

X+

X

X*

)1(

)1()(

)(22

22

cc

HXIXI

c22

c22

= X+)/X+)

= X+)/X+)

Exp.Q

i=35 i=37

I(i C

l+ )/I

(Hi C

l+ )

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-


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(H

35C

l+ )

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.QCalc.V,v´=9

Exp.SCalc.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(H

35C

l+ )

Exp.QCalc.V,v´=9

Exp.SCalc.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´=6J´=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

tens

ity

77.98x10377.9677.9477.9277.9077.8877.86Wavenumber 2hv/cm-1

Q

02489 7 6

E1

79Br

H79Br

10

H79Br

79.8

79.6

79.4

79.2

x103

J´=0

J´=6

J´=9 J´=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

Ene

rgy

3.02.52.01.51.00.5

E(1)

V(m+7)

F(1)

G(C11)

(JL)

(JL)

(JL)(SO)

(SO)

JL

R(t3+1) R(A1, a3)

R(t3+1)

G(C11)

R(A1, a3)

V1+(m+7)

E1+(1)

F1(1)

Ener

gy

(SO)

(JL)(SO)

HBrÁ. Kvaran et al., J. Chem. Physics, 136, 214315,(2012)

-H+ X-

XH

HX**{ }..

HX

:: ::

:: :.

+

-

.

+

“Summary”:

Photodissociation,

State interactions,

Energetics...

::Victor Huasheng Wang

Kristján MatthíassonJingming Long

Helgi Rafn Hróðmarsson

Coworkers:

... HBr,HI..

...HCl, HBr..

.....HCl,....

..RX..

::Kári Sveinbjörnsson

Hafdís Inga Ingvarsdóttir

Eiríkur ÞórirBaldursson

Andras Bodi

Coworkers:

CH3 I

CF 3Br

Ab initio

CH2Br2

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