photofragmentations, state interactions and energetics of halogen containing molecules:...

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 mS

laser control

Pellin Broca prism

SHG control

In

out

REMPI = Resonance Enhanced MultiPhoton Ionization

1xhn

2xhn

2

E

AB

AB+ + e

AB**

(2 + 1) REMPI


1xhn

2xhn

2

E

AB

AB+ + e

AB**

A + B+ + e


1xhn

2xhn

2

E

AB

AB+ + e

AB**

A + B+ + e

AB # #

AB+ + e

A+ + B + e

A + B+ + e

A + B/B*


1xhn

2xhn

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+

30,0323

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+

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 1S+(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

85.3685.3585.3485.33x10

3

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F1D2

2h n / 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) / y0 (2) / y01 2

c1y01

ya

c2y02= +

yb =c1

´y0 c2´y0-

1 2

c1c2+2 2

= 1

E

WEci

2

4

2

12

12

2

2

E

W 12:

Interaction

strength

(1) / y0 (2) / y01 2

c1y01

ya

c2y02= +

yb =c1

´y0 c2´y0-

1 2

c1c2+2 2

= 1

E

WEci

2

4

2

12

12

2

2

E

(1) / y0 (2) / y01 2

c1y01

ya

c2y02= +

yb =c1

´y0 c2´y0-

1 2

c1c2+2 2

= 1

E

WEci

2

4

2

12

12

2

2

E( ) E(J´)DE

E

85.3685.3585.3485.33x10

3

H35Cl+

35Cl+

Q

J´=J´´ = 9 8 7 6 5 4 3 2

HCl, F1D2

2h n / 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

DEJ´=8 =11.3 cm-1

HCl:

F1D2

V1 S

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, F1D2

2h n / 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

DE

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

DEJ´=8 =11.3 cm-1

HCl:

F1D2

V1 S

.6=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*

ac1 b2c2+2 2

I (HX+) =

bc1 a2c2+2 2

I (X+) =

Ry: I.P./V:

)1(

)1(

)(

)(22

22

c

c

HXI

XI

c22

c22

a = a2(X+)/a(HX+)g= b(X+) /a2(X+)

ag= b(X+)/a(HX+)

r(H-X)

E

HX

H+--X-


v´

J´

v´

J´c1

2 c22

X+

X

X*

)1(

)1(

)(

)(22

22

c

c

HXI

XI

c22

c22

a= a2(X+)/a(HX+)

aag

ag= b(X+)/a(HX+)

1 2 3 4 5 6-0.2

-1.66533453693773E-16

0.2

0.4

0.6

0.8

1

1.2

J'

Exp.Q

1 2 3 4 5 60

0.2

0.4

0.6

0.8

1

1.2

J'

i=35 i=37

I(i C

l+)/

I(H

i Cl+

)

Exp.Q

Calc. V,v´ = 20

Calc. V,v´=20

j3S-1; n´=0

isotopomers H35Cl H37ClJ´ closest resonances(J´res) 2 2|DE(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)

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

HiCl j 3S-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 3S-1

t 3S+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 3D2 f 3D1

I(35

Cl+

)/I(

H35

Cl+

)

States f3D2 f3D1

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

max(J´res)/ cm-1 2 4c1

2(J´res) 0.987 0.979a 4.0 0.5ag »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 3D2 f 3D1

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 (1P,3P)”:

0 1 2 3 4 5 6 7 80

0.2

0.4

0.6

0.8

1

1.2

J'

I(37

Cl+

)/I(

H37

Cl+

)

H37Cl j 3S- (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 3S- (0+), v´=0

V 1S(0+)

H37Cl

Near resonance

T SW´=0 W´=0

E/c

m-1

0 1 2 3 4 5 6 7 80

0.2

0.4

0.6

0.8

1

1.2

J'

I(37

Cl+

)/I(

H37

Cl+

)

Calc. V,v´=20 V,v´=21

H37Cl j 3S- (0+)

Exp. Q

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

(J´res) / cm-1 25 25c1

2(J´res) 0.82 (a ag) 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 1S(0+), v´=0

J´=9 v´=m+4

J´=0

V 1S(0+)

Off resonance

S SW´=0 W´=0

J´=6

J´=0

E/c

m-1

0 1 2 3 4 5 6 7 8 90

0.05

0.1

0.15

0.2

0.25

0.3

0.35

J'

0 1 2 3 4 5 6 7 8 90

0.2

0.4

0.6

0.8

1

1.2

1.4

J'

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(C1P1)

(JL)

(JL)

(JL)(SO)

(SO)

JL

R(t3S+1) R(A1P, a3P)

R(t3S+1)

G(C1P1)

R(A1P, a3P)

V1S+(m+7)

E1S+(1)

F1D2(1)

En

erg

y

(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

CH2Br

2

photofragmentations, state interactions and energetics of halogen containing molecules:...

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