HBr / DBr Tunneling vs lifetime calculations &

1. HBr / DBr Tunneling vs lifetime calculations & Excitations according to Castlemann(http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf ) agust,www,.......June11/PPT-111111ak.ppt agust,heima,.....June11/XLS-111111ak.xls agust,heima,....June11/PXP-141111ak.pxp

2. HBr: v´=3 v´=3 v´=2 v´=1 v´=0 0.0351 =a0 V E 0.0725 =a0 0.1121 =a0 DBr: v´=3 v´=2 v´=1 v´=0 0.0713 =a0 V E 0.0976 =a0 0.1255 =a0

3. agust,heima,.....June11/XLS-111111ak.xls

4. HBr: v´=3 v´=3 v´=2 v´=1 v´=0 0.0351 =a0 V E 0.0725 =a0 0.1121 =a0 Try for U0 = E(v=n)-E(v) for n = 1-2, v = 0,1 i.e. 2228 cm-1 <U0< 4334 cm-1 for v´=0 0<U0< 2106 cm-1 for v´=0

5. HBr: For lifetime of v´=0 for E state = 10 ps (according to Castlemanhttp://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf ): NB! According to Long (http://notendur.hi.is/agust/rannsoknir/rempi/hbr/June11/New states summary-290611jl.ppt ) Lifetime for E(v´=0) ³6.491598 ps Lifetime for E(v´=1) ³ 2.31441 to 1.058539 ps Lets try calculations for lifetime E(v´=0 )= 6.5 ps agust,heima,.....June11/XLS-111111ak.xls

6. HBr: For lifetime of v´=0 for E state = 6.5 ps (according to Long): agust,heima,.....June11/XLS-111111ak.xls

7. Our paper, ´98 (http://www.raunvis.hi.is/~agust/rempisvaedidir/jcp109585698.pdf ): DE/cm-1 HBr: Coefficient values ± one standard deviation a = 2339.4 ± 14.9 = we hallat.: b =-116.56 ± 5.44 _ -2*wexe => wexe= 58.28 cm-1 v´+1 agust,heima,....June11/PXP-141111ak.pxp; Gr0, Lay0 agust,heima,.....June11/XLS-111111ak.xls

8. a: http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf agust,heima,.....June11/XLS-111111ak.xls

9. H81Br E-state D81Br E-state v´=3 v´=2 v´=3 Ours v´=2 v´=1 Castlemann´s v´=1 v´=0 v´=0 To=76784.77 Error limits for laser excitations Excitations According to Castlemann 254.7 nm 254.7 nm 255.3 255.3 256.7 256.7 agust,heima,....June11/PXP-141111ak.pxp; Gr1, Lay1

10. Comments: • excitations for H81Br are clearly to v´= 0 • Excitations to D81Br are also primarely to v´= 0 but because of linewidth of laser beam • there is an increasing contribution of excitations to v´= 1 (only) asl = 256.7-> 255.3 -> 254.7 nm but no significant excitation is to v´= 2 ! • The difference in evaluations of energy levels for v´(E) for DBr for me and • Castlemann´s is:- Castlemann relies on the we = 1365 cm-1(?) value according to NISTa • - I evaluate we and we xe for DBr from the corresponding values for H81Br by the relationship • we(2) = we (1)*r and wexe (2) = wexe (1)*r**2 where • and use To evaluated from the HBr parameters • (see: agust,heima,.....June11/XLS-111111ak.xls ) • This strongly suggest s that the barrier is lower than v´= 3 for HBr (which is what Castlemann • suggests (http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf )) a: http://webbook.nist.gov/chemistry/form-ser.html.en-us.en

11. H81Br E-state D81Br E-state v´=3 v´=2 v´=3 Ours v´=2 v´=1 Castlemann´s v´=1 v´=0 825 cm-1 1153/ 1155 cm-1 v´=0 483 cm-1! To=76784.77 Excitations According to Castlemann 254.7 nm 254.7 nm 255.3 255.3 256.7 256.7 agust,heima,....June11/PXP-141111ak.pxp; Gr1, Lay1