HCl, Deperturbation E1, V14, V15 (slides 2-7 ) E0, V10, V11 (slides 8-10 ) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PPT-300712ak.ppt https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp Instruction about how to perform deperturbation calculations: https://notendur.hi.is/jil3/Instruction/Deperturbedprocedure.htm & https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/DOC-020812jla.doc Information sheet (for HCl, Ei; i = 0,1 & V(v´); v = 10,11,14,15): https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/DOC-020812jl.doc

v1,v2,v3 V15 E1 85836 V14 Unrealistic region 123 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:0, Gr:0

HCl, E1, V14, V15 B1 Unrealistic region 123 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:1, Gr:1

HCl, E1, V14, V15 D1 Unrealistic region 123 W/cm-1 =-0.002102 ± 0.00724 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= 5.3194E-4 = 0.53E-3=+0.00053<= NIST) and X(HCl+) (De= 5.477E-4 = 0.547E-3=+0.000547<= NIST ) =-0.021692 ± 0.00629 =-0.03616 ± 0.00592 =-0.050412 ± 0.0058 Unrealistic region =-0.064426 ± 0.00651 123 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:2, Gr:2

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 =6.3818 ± 0.241 =6.8758 ± 0.238 =7.4842 ± 0.271 =8.3171 ± 0.334 =9.978 ± 0.52 =8.5108 ± 6.08 =7.6198 ± 32.8 =9.8162 ± 28.6 =2.2086 ± 0.428 D1 =-0.064426 ± 0.00651 =-0.050412 ± 0.0058 =-0.03616 ± 0.00592 =-0.021692 ± 0.00629 =-0.002102 ± 0.00724 =-0.013809 ± 0.0586 =-0.003957 ± 0.258 =0.022498 ± 0.237 =0.014335 ± 0.00863 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 =6.0986 ± 0.117 =5.949 ± 0.146 =5.5754 ± 0.196 =4.3178 ± 0.384 =5.0287 ± 6.09 =5.7503 ± 31 =4.7002 ± 24.8 =5.9991 ± 0.536 D2 =0.0058507 ± 0.00176 =0.0059503 ± 0.00196 =0.0055398 ± 0.00243 =0.0030923 ± 0.0032 =-0.0090158 ± 0.00543 =0.0070868 ± 0.0719 =0.0091504 ± 0.32 =-0.0074807 ± 0.288 =-0.052407 ± 0.0113 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 ± 0.0864 =4.2778 ± 0.0941 =4.2781 ± 0.113 =4.232 ± 0.139 =4.1278 ± 0.167 =4.0851 ± 0.798 =3.6812 ± 3.39 =2.7625 ± 4.53 =10.108 ± 0.816 D3 =0.00077534 ± 0.00196 =0.0029304 ± 0.00215 =0.0054853 ± 0.00265 =0.0080898 ± 0.00335 =0.011192 ± 0.00416 =0.011843 ± 0.0199 =0.0032304 ± 0.0707 =0.025914 ± 0.262 =0.042671 ± 0.0156 W =25 ± 0 =50 ± 0 =75 ± 0 =100 ± 0 =123 ± 0 =150 ± 0 =175 ± 0 =200 ± 0 =225 ± 0 B0 =10.44 ± 0 D0 =0.000509 ± 0 W12(max)=DE/2 = 246/2= https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

HCl, E1, V14, V15 D1 +0.000596! -6.71E-05 -0.00078 124.6 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:3, Gr:3

HCl, E1, V14, V15 v1 =85853 ± 6.19 =85841 ± 8.22 =85840 ± 8.62 =85838 ± 9.04 =85836 ± 9.55 =85835 ± 10.1 B1 =9.6244 ± 0.462 =10.11 ± 0.549 =10.182 ± 0.566 =10.25 ± 0.584 =10.319 ± 0.606 =10.378 ± 0.628 D1 -0.0057505 -0.00078 -6.71E-05 0.000596 0.001277 0.001846 v2 =85760 ± 4.61 =85773 ± 6.52 =85775 ± 6.9 =85777 ± 7.31 =85779 ± 7.81 =85781 ± 8.31 B2 =4.6323 ± 0.321 =4.1936 ± 0.417 =4.1243 ± 0.437 =4.058 ± 0.456 =3.9883 ± 0.483 =3.9273 ± 0.508 D2 =-0.0057577 ± 0.00473 =-0.010315 ± 0.0058 =-0.011051 ± 0.00603 =-0.011743 ± 0.00623 =-0.012477 ± 0.00654 =-0.013092 ± 0.00683 v3 =86377 ± 1.13 =86375 ± 1.2 =86375 ± 1.22 =86375 ± 1.24 =86375 ± 1.26 =86375 ± 1.28 B3 =4.1458 ± 0.162 =4.1217 ± 0.169 =4.1188 ± 0.171 =4.1159 ± 0.172 =4.1127 ± 0.174 =4.1102 ± 0.176 D3 =0.010639 ± 0.00401 =0.011399 ± 0.00422 =0.011514 ± 0.00426 =0.011625 ± 0.00431 =0.011732 ± 0.00435 =0.011842 ± 0.00442 W 120 124 124.5 125 125.5 126 B0 =10.44 ± 0 D0 =0.000509 ± 0 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

( ): unrealistic points B1 ( ) ( ) ( ) ( ): unrealistic points ( ) D1 => correlation between B1 and D1, i.e. highest B1 value for D1 closest to 0 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:8, Gr:8

HCl, E0, V10, V11 v1,v2,v3 V11 E0 83697 V10 W/cm-1 Unrealistic region https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:7, Gr:7

HCl, E0, V10, V11 B1 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:4, Gr:4

HCl, E0, V10, V11 D1 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:5, Gr:5

HCl, E0, V10, V11 B1 D1 => correlation between B1 and D1, i.e. highest B1 value for D1 closest to 0 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:6, Gr:6

No significant change in D(v1) HCl, E0, V10, V11 B1 D1 W v1 v2 v3 4.9336 -0.059136 150 83765 83513 84154 5.2599 -0.061566 160 83758 83525 84144 7.995 -0.013794 170 83739 83543 84141 7.5216 -0.024466 175 83736 83552 84137 7.6682 -0.01815 180 83727 83566 84134 8.268 -0.0088196 185 83713 83584 84132 8.4503 -0.0065942 186 83708 83588 84131 8.602 -0.0050225 187 83704 83593 8.7473 -0.00438 189 83698 83601 84130 8.7626 -0.0042858 189.1 83697 83602 8.7279 -0.0045835 189.2 8.7793 -0.0042049 189.3 83603 8.7747 -0.0043186 189.4 8.7699 -0.0043748 189.7 83696 83604 84129 8.6616 -0.0057388 190 8.647 -0.0066091 191 83695 83607 84128 8.5023 -0.0088354 192 83609 84127 7.8385 -0.017711 195 83613 84123 dep pert(J´=0) pert-dep. v1(E1;W=125) 85838 85919.4 81.36496 ours v1(E0;) 83697 83780.4 83.43347 D(v1) 2141 2138.931 vi(E0) 83706.9 83780.43 73.53347 Field 2131.1 No significant change in D(v1) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

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

HCl, E1, V14, V15 for W2 = 123 v1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:2, Gr:2

HCl, E1, V14, V15 for W2 = 123 B1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:0, Gr:0

HCl, E1, V14, V15 for W2 = 123 D1 D(D1) = 0 – 0.001 cm-1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:1, Gr:1

HCl, E1, V14, V15 for W2 = 123, W3 CHANGES as above B1 D(D1) = 0 – 0.001 cm-1 D1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:3, Gr:3

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 (= +0.0006 cm-1) -increases B1 from 9.97 to 10,096 cm-1 -causes small increase in v1 ( 85845 -> 85848 cm-1) v1 B1 D1 W2 W3 85845 9.9748 -0.00215 123 85846 10.015 -0.00121 125 85847 10.053 -0.00032 127 85848 10.075 0.000154 128 10.096 0.000609 129 85849 10.116 0.00107 130 85856 10.327 0.005588 140 85868 10.695 0.01259 155 85877 10.986 0.017543 165 85892 11.53 0.025886 180 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

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!

Now let´s check E0,....: Comparison with Fields work: https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp109-8374-98.pdf: Try this

v1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:6, Gr:6

HCl, E0, V10, V11 for W2 = 187 B1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:4, Gr:4

HCl, E0, V10, V11 for W2 = 187 D1 D(D1) = 0 – 0.001 cm-1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:5, Gr:5

HCl, E0, V10, V11 for W2 = 187, W3 CHANGES as above B1 D1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:7, Gr:7

No significant change in D(v1) B1 D1 W2 W3 83704 8.611 -0.00488 187 83707 8.6086 -0.0045 188 83713 8.8675 -0.0008 192 83715 8.9542 -6.81E-05 193 9.0138 0.00038 193.5 83716 9.0665 0.000731 194 83718 9.2962 0.00233 196 83730 9.1723 0.001679 200 83748 8.6123 -0.00223 205 83672 2.7465 -0.08097 231 dep pert(J´=0) pert-dep. v1(E1;W2=123;W3=129) 85848 85919.36 71.36496 v1(E0;W2=187,W3=193.5) 83715 83780.43 65.43347 ours D(v1) 2133 2138.931 v1(E0) 83706.9 73.53347 Field 2141.1 No significant change in D(v1) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

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 = +0.0006 , W2 = 123, W3 = 129 2) E0: B1= 9.01, D1= +0.0004, W2 = 187, W3= 193.5 2) Could it be that W2 <187 and W3 > 193.5 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) = -0.0051 (for W3 = 197) and V1= 83755 (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 = 83700 => no big change in D(v1) & Tried: W2 = 195 and varying W3 > 195 => B1(max)=9.2 for D1(min) = -0.0009 (NB D1 <0, always) V1 = 83709 => no big change in D(v1) Best Results! In agreement with Field et al.! No improvements! See: https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls