1. HBr / DBr Tunneling vs lifetime calculations & Excitations according to Castlemann (http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf )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: E V v´=3 v´=2 v´=1 v´=0 DBr: E V v´=3 v´=2 v´=1 v´=0 84333.3 cm-1(Castleman) /84249.5 (ours,´98) 84333.3 cm-1 77267.88=>U0=7065.4 78840.66=>U0=5492.6 80324.72=>U0= 4008.6 77939.5 (ours,´98) 6310 (ours,´98) 0.1255 =a 0 0.0976 =a 0 0.0713 =a 0 4082 (ours,´98) 1976 (ours,´98) 0.1121 =a 0 0.0725 =a 0 0.0351 =a 0

3. HBr:Castlemann: Ours(´98): vE/eVE/cm-1 U0=E(v=3)-E(v)ao/A 09.66377937.3220177939.563100.112146987 19.93980163.411380167.540820.07254897 210.282268.5174982273.519760.035119247 310.45684333.2959684249.500 410.67986131.91159 from a0(A) used tocastelman´sNB!: DBrderive same lifet.paper:Calc. vas in paperLifetimes(ps)E(v)/eVE(v)/cm-1U0=E(HBr,v=3)-E(v)/cm-1a0/nma0/mU0/kJ mol-1U0/Ja (m/(Js))lifet(s)lifet (ps)U0/a0 (J/m)U0/a0(cm-1/nm) 00.125520109.5877267.882117065.4138550.012551.26E-118.45E+011.40E-191.19E+232.01E-092.01E+031.1184E-0856298.11836 10.097657.29.77578840.662595492.6333730.009769.76E-126.57E+011.09E-199.25E+225.72E-115.72E+011.1179E-0856276.98128 20.07133.19.95980324.722124008.5738420.007137.13E-124.80E+017.96E-206.76E+223.10E-123.10E+001.1168E-0856221.23201 310.1481784.585032548.7109343.05E+015.06E-20 : is constantca. constant HBr, v=310.45684333.29596average:1.1177E-0856265.44389 agust,heima,.....June11/XLS-111111ak.xls

4. HBr: E V v´=3 v´=2 v´=1 v´=0 84333.3 cm-1(Castleman) /84249.5 (ours,´98) 77939.5 (ours,´98) 6310 (ours,´98) 4082 (ours,´98) 1976 (ours,´98) 0.1121 =a 0 0.0725 =a 0 0.0351 =a 0 Try for U 0 = 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 U0=E(v=1)-E(v)U0=E(v=2)-E(v)v 222843340 021061 02

5. Ebarrier Uo(v´=0)/cm-1Uo(v´=1)/cm-1Uo(v´=0)/JU0(v´=1)/Jao(v=0)/mao(v=0)/AUo(v´=0)/ao(v=0)(J/m)ao(v=1)/mao(v=1)/At(v=1)/s t(v=1)/ps 80167.5 222804.43E-200.00E+001.80E-111.80E-012.45E-090.00E+00 1.50E-14 1.50E-02 80439.5 25002724.97E-205.40E-211.70E-111.70E-012.92E-091.85E-121.85E-021.90E-14 1.90E-02 80639.5 27004725.36E-209.38E-211.64E-111.64E-013.27E-092.86E-122.86E-022.42E-14 2.42E-02 80839.5 29006725.76E-201.33E-201.58E-111.58E-013.64E-093.66E-123.66E-023.10E-14 3.10E-02 81039.5 31008726.16E-201.73E-201.53E-111.53E-014.03E-094.30E-124.30E-023.96E-14 3.96E-02 81239.5 330010726.56E-202.13E-201.48E-111.48E-014.42E-094.82E-124.82E-025.01E-14 5.01E-02 81439.5 350012726.95E-202.53E-201.44E-111.44E-014.83E-095.23E-125.23E-026.24E-14 6.24E-02 81639.5 370014727.35E-202.92E-201.40E-111.40E-015.25E-095.57E-125.57E-027.68E-14 7.68E-02 81839.5 390016727.75E-203.32E-201.36E-111.36E-015.68E-095.85E-125.85E-029.32E-14 9.32E-02 82039.5 410018728.14E-203.72E-201.33E-111.33E-016.12E-096.07E-126.07E-021.12E-13 1.12E-01 82239.5 430020728.54E-204.12E-201.30E-111.30E-016.58E-096.26E-126.26E-021.32E-13 1.32E-01 82273.5 433421068.61E-204.18E-201.29E-111.29E-016.66E-096.29E-126.29E-021.36E-13 1.36E-01 HBr: For lifetime of v´=0 for E state = 10 ps (according to Castleman http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf ): http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf agust,heima,.....June11/XLS-111111ak.xls NB! According to Long ( http://notendur.hi.is/agust/rannsoknir/rempi/hbr/June11/New states summary-290611jl.ppt ) http://notendur.hi.is/agust/rannsoknir/rempi/hbr/June11/New states summary-290611jl.ppt Lifetime for E(v´=0)  6.491598 ps Lifetime for E(v´=1)  2.31441 to 1.058539 ps Lets try calculations for lifetime E(v´=0 )= 6.5 ps

6. HBr: For lifetime of v´=0 for E state = 6.5 ps (according to Long): agust,heima,.....June11/XLS-111111ak.xls Ebarrier Uo(v´=0)/cm-1Uo(v´=1)/cm-1Uo(v´=0)/JU0(v´=1)/Jao(v=0)/mao(v=0)/AUo(v´=0)/ao(v=0)(J/m)ao(v=1)/mao(v=1)/At(v=1)/s t(v=1)/ps 80167.5 222804.43E-200.00E+001.68E-111.68E-012.63E-090.00E+00 1.50E-14 1.50E-02 80439.5 25002724.97E-205.40E-211.59E-111.59E-013.12E-091.73E-121.73E-021.87E-14 1.87E-02 80639.5 27004725.36E-209.38E-211.53E-111.53E-013.51E-092.67E-122.67E-022.34E-14 2.34E-02 80839.5 29006725.76E-201.33E-201.48E-111.48E-013.90E-093.42E-123.42E-022.96E-14 2.96E-02 81039.5 31008726.16E-201.73E-201.43E-111.43E-014.31E-094.02E-124.02E-023.72E-14 3.72E-02 81239.5 330010726.56E-202.13E-201.38E-111.38E-014.74E-094.50E-124.50E-024.62E-14 4.62E-02 81439.5 350012726.95E-202.53E-201.34E-111.34E-015.17E-094.88E-124.88E-025.68E-14 5.68E-02 81639.5 370014727.35E-202.92E-201.31E-111.31E-015.62E-095.20E-125.20E-026.89E-14 6.89E-02 81839.5 390016727.75E-203.32E-201.27E-111.27E-016.09E-095.46E-125.46E-028.26E-14 8.26E-02 82039.5 410018728.14E-203.72E-201.24E-111.24E-016.56E-095.67E-125.67E-029.77E-14 9.77E-02 82239.5 430020728.54E-204.12E-201.21E-111.21E-017.04E-095.84E-125.84E-021.14E-13 1.14E-01 82273.5 433421068.61E-204.18E-201.21E-111.21E-017.13E-095.87E-125.87E-021.17E-13 1.17E-01

7. Our paper, ´98 (http://www.raunvis.hi.is/~agust/rempisvaedidir/jcp109585698.pdf ):http://www.raunvis.hi.is/~agust/rempisvaedidir/jcp109585698.pdf  E/cm -1 v´+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 D81Br: m(reduced mass)1.965185984g mol-1  ((1)/(2)) 0.711709632  **2 0.5065306 we(E, D81Br)1664.973512cm-1 wexe(E,D81Br)29.52060336cm-1 agust,heima,.....June11/XLS-111111ak.xls agust,heima,....June11/PXP-141111ak.pxp; Gr0, Lay0

8. excitations according to Castlemann a : l / nmE(exc.)2*E(exc.)l lowl highE highE lowE high-E lowEt highEt low 256.1nm39047.2471778094.49434264.1248.140306.3337864.452441.88280879315.4476873.55 255.3nm39169.6043978339.20877263.3247.340436.7237979.492457.22546479567.8277110.6 254.7nm39261.8767278523.75344262.7246.740535.0638066.242468.8275879758.1777289.34 2455.978617 agust,heima,.....June11/XLS-111111ak.xls a: http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdfhttp://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf

9. 256.7 255.3 254.7 nm 256.7 255.3 254.7 nm Ours Castlemann´s H 81 Br E-state D 81 Br E-state Excitations According to Castlemann To=76784.77 agust,heima,....June11/PXP-141111ak.pxp; Gr1, Lay1 v´=0 v´=1 v´=2 v´=3 v´=0 v´=1 v´=2 v´=3 Error limits for laser excitations

10. Comments: excitations for H 81 Br are clearly to v´= 0 Excitations to D 81 Br are also primarely to v´= 0 but because of linewidth of laser beam there is an increasing contribution of excitations to v´= 1 (only) as  = 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  e = 1365 cm -1 (?) value according to NIST a - I evaluate  e and  e x e for DBr from the corresponding values for H 81 Br by the relationship  e (2) =  e (1)*  and  e x e (2) =  e x e (1)*  **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 ))http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf a: http://webbook.nist.gov/chemistry/form-ser.html.en-us.enhttp://webbook.nist.gov/chemistry/form-ser.html.en-us.en

11. 256.7 255.3 254.7 nm 256.7 255.3 254.7 nm Ours Castlemann´s H 81 Br E-state D 81 Br E-state Excitations According to Castlemann To=76784.77 agust,heima,....June11/PXP-141111ak.pxp; Gr1, Lay1 v´=0 v´=1 v´=2 v´=3 v´=0 v´=1 v´=2 v´=3 483 cm -1 ! 825 cm -1 1153/ 1155 cm -1