Off-resonance interaction between E and V state of HCl and HBr

Jingming Long

22/09/2011

Near-resonance interaction

Off-resonance interaction

Heterogeneous (>0)Homogeneous (=0)

Rydberg and ion-pair interaction

V1+E1+

j3- f3

E1+ …

H*+X or H+X*

H++X-

Rydberg state

Ion pair state

From ground state

H+X*

HX*

H*+X

HX**X+ H+

HX+

2

1X+ H+HX+

12

02

01 21

cca 0

10

2 21 ccb

222

21 1

)( ccHXI

211

22 2

)( ccXI

BrClX ,

0

1 0

2

1

2

2

1

1

21

10-1<<10 ~0 ~1

||2

||4)(

2

1 212

22

2,1 E

WEci

12

221 cc

)1(

))1((

)(

)(2

22

2c

c

HXI

XI

})1(

)]1([

)1(

)]1([{

)(

)(2,0

2,0

2,0

2,0

j

j

i

i

c

c

c

c

HXI

XI

)}||4()||4{(* 2,0

2,0,0

2,0

2,0,0

~

jjjiii WEEWEEE

Linewidth:

Relative signal Intensity ratio:

Kristján Matthíasson, Jingming Long, Huasheng Wang, and Ágúst Kvaran. “Two-dimensional resonance enhanced multiphoton ionization of HiCl:i = 35, 37: State interactions, photofragmentations and energetics of high energy Rydberg states”[J], J.Chem.Phys. (2011)

Near-resonance interactionHomogeneous perturbation

H35Cl H37Cl

Near-resonance interactionheterogeneous perturbation

Ágúst Kvaran, Kristján Matthiasson, and Huasheng Wang. “Two-dimensional „2+n… resonance enhanced multiphoton ionization of HCl:State interactions and photorupture channels via low-energy triplet Rydberg states”[J]. J.Chem.Phys.131.044324(2009)

HCl

E1+(v’=1)

V1+(v’=15)

V1+(v’=14)

V1+(v’=10)

E1+(v’=0)

V1+(v’=11)

Off-resonance interactionHomogeneous perturbation

400x103

300

200

100

0

Rel

ativ

e In

tens

ity a

.u.

84.2x10384.083.883.683.483.2

Wavenumber /cm-1

Q

V1

v'=10) V

1

v'=11)

Q02468 2 046810

E1

v'=0)

0246810Q

S

O

H35Cl+

35Cl+

H37Cl+

37Cl+

H+

E(E0-V10) E(V11-E0)345.9382 424.22353

348.88047 420.06753353.73699 414.56881

363.2478 404.11409  388.52561  369.807  352.7285  339.09694

W10: 172cm-1 W11 :160cm-1

: 0.6

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

I(35

Cl+

)/I(

H35

Cl+

)

0 1 2 3 4 6 7 8J'

Experiment Calculation

c2=1/2

3x106

2

1

0

-1

-2

Rel

ativ

e In

ten

sity

86.4x10386.286.085.885.6

Wavenumber 2hv/cm-1

86.0085.9585.9085.8585.80

x103

35Cl+

H35Cl+

Q

QQ 05

0

0

2468

V1

E1

V1

86.6x103

86.4

86.2

86.0

85.8

En

erg

y /

cm

-1

V1

'=14)

V1

'=15)

E1

'=1)

J '=0123

4

5

J '=01234

5

6

7

J '=0123456

E1+(v’=1)

W14 : 123cm-1 W15 :120cm-1

: 1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

I(35

Cl+

)/I(

H35

Cl+

)

0 1 2 3 4 5J'

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Experiment From V(v'=14) From V(v'=15)

c2=1/2

: 0

HBr

E1+(v’=1)

V1+(v’=m+9)

V1+(v’=m+8)

V1+(v’=m+4)

E1+(v’=0)

V1+(v’=m+5)

Off-resonance interactionHomogeneous perturbation

300x103

200

100

0

-100

-200

Re

lati

ve

Inte

ns

ity

77.98x10377.9677.9477.9277.9077.8877.86

Wavenumber 2hv/cm-1

Q

02489 7 6

E1

79Br

H79

Br

10

300x103

250

200

150

100

Rel

ativ

e In

ten

sity

77.85x10377.8077.7577.7077.6577.6077.55

Wavenumber 2hv /cm-1

0

Q

12345678

V1m+4)

E10-0) O

79Br

H79

Br

400x103

300

200

100

0

Rel

ati

ve

Inte

ns

ity

77.98x10377.9677.9477.9277.9077.8877.86

Wavenumber 2hv/cm-1

H+

79Br

+

H79

Br+

81Br

+

H81

Br+

E1+(v’=0)

79.8x103

79.6

79.4

79.2

Ener

gy L

evel

E1

V1

m+5)

V1

m+4)

J'=012

3

4

5

6

7

8

9

J'=02

4

5

6

7

8

9

J'=02

4

6

5

3

*Calculation

J’ E(0-m+4) E(0-m+5)

0 110.8 447.81 119.3 441.22 133.4 425.43 155.1 405.6

4 184.6 375.009

5 219.3 333.52

6 266 302.249

7 322.3 266*8 379 235*9 438.8 200*

E1+(v’=0)

W1,m+4: 31cm-1 W1,m+5: 45cm-1: 1.8 : 0.026

0.30

0.25

0.20

0.15

0.10

0.05

0.00

I(79

Br+

)/I(

H79

Br+

)

1 2 3 4 5 6 7 8 9J'

0.30

0.25

0.20

0.15

0.10

0.05

0.00

Experiment From V(v'=m+4) From V(v'=m+5)

Comparison of the linewidth between experiment and calculation

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Lin

ewid

th

/cm

-1

1 2 3 4 5 6 7 8 9J'

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Experiment From V(v'=m+4) From V(v'=m+5)

E1+(v’=0)

600x103

400

200

0

Rel

atvi

e In

tens

ity

80.2x10380.180.079.9

Wavenumber 2hv/cm-1

Q0123456

E1

79Br

H79

Br

V1

(v'=m+8)

Q01234567

2.5

2.0

1.5

1.0

0.5

0.0

I(79

Br+

)/I(H

79Br+

)

0 1 2 3 4 5 6 7J '

2.5

2.0

1.5

1.0

0.5

0.0

Experiment From V(v'=m+8) From V(v'=m+9)

W1,m+8: 53cm-1 W1,m+9: 58cm-1

: 8.4 : 0.03

E1+(v’=1)

HCl HBr

E1+(v’=0) Intensity ratios for low J’ are flat.

Calculation is not good agree with experiment.

Linewidths are more broadening than HCl which have the same

trend as intensity ratios.Calculation is good agree

with experiment.

E1+(v’=1) Intensity ratios for low J’ are flat.

Calculation is good agree with experiment.

Linewidths broadening can’t be explained at

present.Suposed it’s due to predissociation and

tunneling.Calculation is good agree

with experiment.

Summary

Thank you