1 / 29

HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper)

HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www, ....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp (R-C spectrum)

nhu
Download Presentation

HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper)

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www, ....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp (R-C spectrum) agust,heima,...Sept10/XLS-141210ak.xlsagust,heima,...Sept10/XLS-151210ak.xlsagust,heima,...Sept10/XLS-161210ak.xls agust,heima,...Sept10/22320_22356-161210ak.pxp (new R-T spectrum) agust, heima,...Sept10/J3S_V1S21-171210ak.pxp (new R-T spectrum) agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxpagust,heima,...Sept10/XLS-201210ak.xls agust,heima,...Sept10/Look for J7-201210.pxp

  2. JMS, 228,143,(2004)-assignment KM´s assignment REMPI-current agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 5, Gr:2_1

  3. JMS, 228,143,(2004)-assignment 9 6 8 4 3 2 1 0 KM´s assignment 5 7 agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp (R-C spectrum), Lay:2, Gr:1

  4. NB!: KM´s (REMPI-TOF; R-T) spectrum is a lot colder than the JMS (20014)-REMPI- current (R-C) spectrum

  5. Now lets try • Derive Energy level values both from R-T and R-C spectra using • KM´s assignment and check shifts. • 2) Insert Wangs and Longs´newest spectra uncluding “newly observed “ • peaks for comparison. from KM: Slide 7 Slide 6 agust,heima,...Sept10/XLS-151210ak.xls

  6. From REMPI-TOF (KM): E(J´) Coefficient values ± one standard deviation K0=C = 89281 ± 3.56 K1=B´ = 9.7179 ± 0.229 K2=D´ = 0.0026284 ± 0.0026 J´=9 J´=7 J´=6 J´(J´+1) agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 7, Gr:11

  7. From REMPI-TOF (KM): DE J´,J´-1 23.78 4.8436663 cm-1 agust,heima,...Sept10/XLS-151210ak.xls = 19.497 J´ = 2B´J´=> B´= 9.7485 cm-1 J´ agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 6, Gr:9

  8. Now let´s look at the latest data for V, v´=21 from Long and Wang: I will wait for Longs analysis and summaries of mass spectra vs REMPI peaks

  9. Let´s look at the REMPI-current data Let´s look at energy levels or the V, v´=21 state: Is there a shift of levels to be found?

  10. V,v´=21, J´=6 i=35 i=37 H+ agust,heima,...Sept10/22320_22356-161210ak.pxp, Lay:0, Gr:1

  11. agust,heima,...Sept10/XLS-161210ak.xls

  12. From REMPI-TOF (VHW&JL): DE J´,J´-1 24.95 cm-1 agust,heima,...Sept10/XLS-151210ak.xls = 6.8778 J´ = 2B´J´=> B´= 3.4389 cm-1 J´ agust,heima,...Sept10/22320_22356-161210ak.pxp, Lay:1, Gr:2

  13. (W&L´s observation for J´=6 (V)(?): n(J’=6;V)-n(J´=6,j)=90.8 cm-1) KM´s prediction, assuming n(J’=6;V)-n(J´=6,j)=64cm-1 NB!: According to KM (211210) the peak at 22334.27 89337.08 is a S line peak for V!! The broad peaks However might be V,v´=21, J´=6 agust,heima,...Sept10/22320_22356-161210ak.pxp, Lay:0, Gr:1

  14. agust,heima,...Sept10/XLS-161210ak.xls

  15. W12 dervid from J´=6 NB! Not needed in calculation of W12 (see below) (E2 (6) = 89774.7 ) ? 24.95cm-1 J´(V, v´=21) = 6 E20(6) = 89749.7 89719.2 cm-1 4.84 cm-1 89688.7 = E10(6) J´(j, v´=0) = 6 89683.9 = E1 (6) agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 8, Gr:12

  16. W12 derived from J´=7 : DE J´,J´-1 V,v´=21 state data This is slightly underestimated value This is largely overestimated value J´ agust,heima,...Sept10/22320_22356-171210ak.pxp, Lay:1, Gr:2

  17. The large difference in W12 obtained for J´= 6 and 7 suggests that the Line assignment for j<-<-X is wrong(?). Let´s check other possibilities. 1) OLD assignment: NO evaluation method is no good!

  18. Old assignment 20.707 3.27 j,v´=0 state data

  19. OLD assignment gives largest gap for J´=7 <->J´=8 whereas KM´s assignment gives largest gap for J´=6 <->J´=7 Is it possible to find largest gap for J´=5 <->J´=6? That would fit with the V, v´= 21 gap / shifts! ATH! Larger Cl+/HCl+ ratios according to KM = j state peaks Large gap: 6<->7 7<->8 5<->6 5<->6 6<->7 6<->7 KM: 9 6 8 5 7 4 3 2 1 0 OLD: 10 11 9 7 8 6 5 4 3 2 1 AK(1) 9 5 7 8 6 4 3 2 1 0 AK(2) 9 5 8 7 6 4 3 2 1 0 AK(3) 8 - 6 - 5 7 4 3 2 1 0 AK(4) 9 6 6/8 5 5 7 4 3 2 1 0 NO! 9 10 J(1);S i=37 overlap

  20. AK(1) assignment: NO! agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 10, Gr:14

  21. Could be 37 peak from V, v´=21 J, v´=0 H37Cl+ 35Cl+ H35Cl+ H+ 1hv agust, heima,...Sept10/J3S_V1S21-171210ak.pxp; Lay: 2, Gr: 1

  22. AK(2) assignment (see slide 19): NO! agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 11 Gr:15

  23. Energy levels (E(J´): J(0+)-state <= KM V,v´=21 state 13.018 cm-1 J´=7 89844.13475 J´=7 89799.8784 89828.476 J´=6 J´=6 agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 12, Gr:16 and .....Sept10/XLS-201210ak.xls

  24. AK(3) assignment (see slide 19): agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 13 Gr:17

  25. J(0+)-state <= AK(3) 12.298 cm-1 V,v´=21 state J´=7 J´=6 agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 12, Gr:16 and .....Sept10/XLS-201210ak.xls

  26. Now it is possible to predict the position of the J´=9 band agust,heima.....Sept10/XLS-201210ak.xls

  27. J(0+)-state <= AK(3) Fits nicely J´=7 J´=6 agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 12, Gr:16 and .....Sept10/XLS-201210ak.xls

  28. 5 6 7 8 9 5 9 7 6 8 4.02 This could be V, v´=21, J´=7(?) agust,heima,...Sept10/Look for J7-201210.pxp

  29. See also figs in KM´s manuscript and my comments there. It is worth performing some isotopomer calculations NB! According to Longs estimate (agust,heima,..../Sept10/V state V21q energy diference between H35Cl and H37Cl-141210jl-201210ak.xls) The isotope separation for J´= could be < 5. Now let´s check where exactly j(1), S serie peak is to be found.

More Related