perturbation simulation assuming interactions: v,v´=11 g 3 s - v,v´=10 g 3 s - by pippa 1132...

Perturbation simulation assuming interactions:V,v´=11 <-> g3-

V,v´=10 <-> g3-

V,v´=09 <-> g3-

Ref.:Agust,www,....rempi/hcl/October08/HClg3S-V8-11-041108ak.ppt Agust,heima,..October08/Term values for triplet paper-041108kmak.xlsAgust,heima,... kennsla/ArnarH/IGOR/Profun-041108ahak.pxp &Agust,heima,... kennsla/ArnarH/IGOR/Profun-041108ahaka.pxp

Agust,heima,... kennsla/ArnarH/IGOR/Profun-041108ahaka.pxp

Deperturbed levels according toD. Field et al.

84.0x103

83.5

83.0

82.5

2 h

[cm

-1]

g3-

(0+) , v'=0

V1+

, v'=9

V1+

, v'=10J'0

123

4

0

0

1

1

2

2

3

3

4

5

5

6

J'

J'

V1+

, v'=8

V1+

, v'=11

calculated levels:Using W12(v´=9) =359 cm-1 & W12(v´=10) = 520 cm-1

And W12(v´=11) = 602 cm-1

And equation:

2/120

201

2

1202

01 )(4

2

1

2

1EEWEEEi

Perturbed levels (<= Green et al.)

Agust,heima,... kennsla/ArnarH/IGOR/Profun-041108ahak.pxp

84.0x103

83.5

83.0

82.5

2 h

[cm

-1]

g3-

(0+) , v'=0

V1+

, v'=9

V1+

, v'=10J'0

123

4

0

0

1

1

2

2

3

3

4

5

5

6

J'

J'

V1+

, v'=8

V1+

, v'=11

W12(v´=11) = 602 cm-1

W12(v´=10) = 520 cm-1

W12(v´=9) =359 cm-1

Agust,heima,... kennsla/ArnarH/IGOR/Profun-041108ahaka.pxp

NB!:Quite large shift of levels due toThe v´=11 <-> g3-

interaction

“shifted Levels”

Deperturbed levels according to

D. Field et al.

Least Square W(9) W(10) W(11)

11817.7 266 589 6005968.42 266 550 60054.0351 266 450 60043.8474 281 470 60019.2466 339 510 60015.136 339 510 60214.0797 342 513 60213.8098 343 514 60213.3903 345 516 60212.9533 348 518 60212.4934 359 520 602

Agust,heima,... kennsla/ArnarH/IGOR/Profun-041108ahak.pxp:

Summary:

Reasonably good fit can be obtained to perturbed levels for g3- by assuming:

W(v´=9)/cm-1

W(v´=10)/ cm-1

W(v´=11)/ cm-1

266 589 0 1)

359 520 602

1) see: agust,www,....rempi/hcl/October08/HClg3S-V9V10-031108ak.ppt