1. HCl, Deperturbation
E1, V14, V15 (slides 2-7 )
E0, V10, V11 (slides 8-10 )
Instruction about how to perform deperturbation calculations:
&
Information sheet (for HCl, Ei; i = 0,1 & V(v´); v = 10,11,14,15):

2. v1,v2,v3 V15 E1 85836 V14 Unrealistic region 123 W/cm-1
Lay:0, Gr:0

3. HCl, E1, V14, V15 B1 Unrealistic region 123 W/cm-1
Lay:1, Gr:1

4. HCl, E1, V14, V15 D1 Unrealistic region 123 W/cm-1
= ±
Deviation of D1 from 0 is a resonable
measure of distortion, i.e. one might
expect D1 (unperturbed) to be close
to zero analogous to that for
X(HCl) (De= E-4 = 0.53E-3= <= NIST) and
X(HCl+) (De= 5.477E-4 = 0.547E-3= <= NIST )
= ±
= ±
= ±
Unrealistic region
= ±
123
W/cm-1
Lay:2, Gr:2

5. HCl, E1, V14, V15 v1
=85917 ± 1.87
=85912 ± 2.06
=85902 ± 2.57
=85884 ± 3.56
=85845 ± 7.54
=85842 ± 123
=85888 ± 704
=85954 ± 717
=86200 ± 2.89 B1
= ± 0.241
= ± 0.238
= ± 0.271
= ± 0.334
=9.978 ± 0.52
= ± 6.08
= ± 32.8
= ± 28.6
= ± 0.428 D1
= ±
= ±
= ±
= ±
= ±
= ±
= ± 0.258
= ± 0.237
= ± v2
=85674 ± 1.17
=85682 ± 1.31
=85697 ± 1.64
=85722 ± 2.34
=85770 ± 5.87
=85810 ± 115
=85822 ± 612
=85838 ± 520
=85814 ± 4.97 B2
=6.162 ± 0.106
= ± 0.117
=5.949 ± 0.146
= ± 0.196
= ± 0.384
= ± 6.09
= ± 31
= ± 24.8
= ± 0.536 D2
= ±
= ±
= ±
= ±
= ±
= ±
= ± 0.32
= ± 0.288
= ± v3
=86403 ± 0.643
=86399 ± 0.695
=86393 ± 0.817
=86384 ± 0.973
=86376 ± 1.18
=86360 ± 10.6
=86336 ± 93
=86286 ± 190
=85977 ± 7 B3
=4.256 ±
= ±
= ± 0.113
=4.232 ± 0.139
= ± 0.167
= ± 0.798
= ± 3.39
= ± 4.53
= ± 0.816 D3
= ±
= ±
= ±
= ±
= ±
= ±
= ±
= ± 0.262
= ± W
=25 ± 0
=50 ± 0
=75 ± 0
=100 ± 0
=123 ± 0
=150 ± 0
=175 ± 0
=200 ± 0
=225 ± 0 B0
=10.44 ± 0 D0
= ± 0
W12(max)=DE/2 = 246/2=

6. HCl, E1, V14, V15 D1 !
-6.71E-05
124.6
W/cm-1
Lay:3, Gr:3

7. HCl, E1, V14, V15 v1
=85853 ± 6.19
=85841 ± 8.22
=85840 ± 8.62
=85838 ± 9.04
=85836 ± 9.55
=85835 ± 10.1 B1
= ± 0.462
=10.11 ± 0.549
= ± 0.566
=10.25 ± 0.584
= ± 0.606
= ± 0.628 D1
-6.71E-05 v2
=85760 ± 4.61
=85773 ± 6.52
=85775 ± 6.9
=85777 ± 7.31
=85779 ± 7.81
=85781 ± 8.31 B2
= ± 0.321
= ± 0.417
= ± 0.437
=4.058 ± 0.456
= ± 0.483
= ± 0.508 D2
= ±
= ±
= ±
= ±
= ±
= ± v3
=86377 ± 1.13
=86375 ± 1.2
=86375 ± 1.22
=86375 ± 1.24
=86375 ± 1.26
=86375 ± 1.28 B3
= ± 0.162
= ± 0.169
= ± 0.171
= ± 0.172
= ± 0.174
= ± 0.176 D3
= ±
= ±
= ±
= ±
= ±
= ± W
120
124
124.5
125
125.5
126 B0
=10.44 ± 0 D0
= ± 0

8. ( ): unrealistic pointsB1
( )
( )
( )
( ): unrealistic points
( ) D1
=> correlation between B1 and D1, i.e. highest B1 value for D1 closest to 0
Lay:8, Gr:8

9. HCl, E0, V10, V11 v1,v2,v3 V11 E0 83697 V10 W/cm-1 Unrealistic region
Lay:7, Gr:7

10. HCl, E0, V10, V11 B1
W/cm-1
Lay:4, Gr:4

11. HCl, E0, V10, V11 D1
W/cm-1
Lay:5, Gr:5

12. HCl, E0, V10, V11 B1 D1
=> correlation between B1 and D1, i.e. highest B1 value for D1 closest to 0
Lay:6, Gr:6

13. No significant change in D(v1)
HCl, E0, V10, V11 B1 D1 W v1 v2 v3
4.9336
150
83765
83513
84154
5.2599
160
83758
83525
84144
7.995
170
83739
83543
84141
7.5216
175
83736
83552
84137
7.6682
180
83727
83566
84134
8.268
185
83713
83584
84132
8.4503
186
83708
83588
84131
8.602
187
83704
83593
8.7473
189
83698
83601
84130
8.7626
189.1
83697
83602
8.7279
189.2
8.7793
189.3
83603
8.7747
189.4
8.7699
189.7
83696
83604
84129
8.6616
190
8.647
191
83695
83607
84128
8.5023
192
83609
84127
7.8385
195
83613
84123
dep
pert(J´=0)
pert-dep.
v1(E1;W=125)
85838
ours
v1(E0;)
83697
D(v1)
2141
vi(E0)
Field
2131.1
No significant change in D(v1)

14. Let´s perform dep. calculations for different W´s
(i.e. WH ¹ WL) for E1,V14, V15:

15. HCl, E1, V14, V15 for W2 = 123 v1
W3 / WH
Lay:2, Gr:2

16. HCl, E1, V14, V15 for W2 = 123 B1
W3 / WH
Lay:0, Gr:0

17. HCl, E1, V14, V15 for W2 = 123 D1 D(D1) = 0 – 0.001 cm-1 W3 / WH
Lay:1, Gr:1

18. HCl, E1, V14, V15 for W2 = 123, W3 CHANGES as above B1
D(D1) = 0 – cm-1 D1
Lay:3, Gr:3

19. Only small increase in W3 from 123 to about 129 (for W2 = 123)
HCl, E1, V14, V15 for W2 = 123, W3 CHANGES
Only small increase in W3 from 123 to about 129 (for W2 = 123)
-improves D1 (= cm-1)
-increases B1 from 9.97 to 10,096 cm-1
-causes small increase in v1 ( > cm-1) v1 B1 D1 W2 W3
85845
9.9748
123
85846
10.015
125
85847
10.053
127
85848
10.075
128
10.096
129
85849
10.116
130
85856
10.327
140
85868
10.695
155
85877
10.986
165
85892
11.53
180

20. I tried
–to fix D1, and to vary W2 & W3 => W2 = 123 W3 = 110 +/- big error (typically)!
- to use W2 = 125 and to vary W3 => W3 ca. 125 best!

21. Now let´s check E0,....:
Comparison with Fields work:
Try this

22. v1
W3 / WH
; Lay:6, Gr:6

23. HCl, E0, V10, V11 for W2 = 187 B1
W3 / WH
; Lay:4, Gr:4

24. HCl, E0, V10, V11 for W2 = 187 D1 D(D1) = 0 – 0.001 cm-1 W3 / WH
; Lay:5, Gr:5

25. HCl, E0, V10, V11 for W2 = 187, W3 CHANGES as above B1D1
; Lay:7, Gr:7

26. No significant change in D(v1)B1 D1 W2 W3
83704
8.611
187
83707
8.6086
188
83713
8.8675
192
83715
8.9542
-6.81E-05
193
9.0138
193.5
83716
9.0665
194
83718
9.2962
196
83730
9.1723
200
83748
8.6123
205
83672
2.7465
231
dep
pert(J´=0)
pert-dep.
v1(E1;W2=123;W3=129)
85848
v1(E0;W2=187,W3=193.5)
83715
ours
D(v1)
2133
v1(E0)
Field
2141.1
No significant change in D(v1)

27. 2) Could it be that W2 <187 and W3 > 193.5 For E0, V10,V11?
Now it looks like:
1) E1: B1= 10.10, D1 = , W2 = 123, W3 = 129
2) E0: B1= 9.01, D1= , W2 = 187, W3= 193.5
2) Could it be that W2 <187 and W3 > For E0, V10,V11?
Search for D1 <0.001 and B1 > 9.01 for E0, V10,V11
=>
By trying W2 =180 and varying W3 > 180 =>
B1(max)= 8.37 only for D1(min) = (for W3 = 197) and
V1= (which is even higher and makes D(v1) still smaller
Ergo: this is not convincing
Could W2 > 187 and W3 still higher?
Tried: W2=190 and varying W3 >190 => B1(max)= 9.1 for D1(min) = 0 (for W3 = 193) and
V1 = => no big change in D(v1)
&
Tried: W2 = 195 and varying W3 > 195 => B1(max)=9.2 for D1(min) = (NB D1 <0, always) V1 = => no big change in D(v1)
Best
Results!
In agreement with Field et al.!
No improvements!
See: