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.pptagust,heima,.....June11/XLS-111111ak.xlsagust,heima,....June11/PXP-141111ak.pxp

HBr:

E V

v´=3v´=3v´=2

v´=1v´=0

DBr:

E V

v´=3v´=2

v´=1v´=0

84333.3 cm-1(Castleman) /84249.5 (ours,´98)

84333.3 cm-1

77267.88=>U0=7065.478840.66=>U0=5492.6

80324.72=>U0= 4008.6

77939.5 (ours,´98) 6310 (ours,´98)

0.1255 =a0

0.0976 =a0

0.0713 =a0

4082 (ours,´98) 1976 (ours,´98)

0.1121 =a0

0.0725 =a0

0.0351 =a0

HBr: Castlemann: Castlemann: Ours(´98):v E/eV E/cm-1 E/cm-1 U0=E(v=3)-E(v) ao/A

0 9.663 77937.32201 77939.5 6310 0.1121469871 9.939 80163.4113 80167.5 4082 0.072548972 10.2 82268.51749 82273.5 1976 0.0351192473 10.456 84333.29596 84249.5 0 04 10.679 86131.91159

froma0(A) used to castelman´s NB!:

DBr derive same lifet. paper: Calc.

v as in paper Lifetimes(ps) E(v)/eV E(v)/cm-1 U0=E(HBr,v=3)-E(v)/cm-1 a0/nm a0/m U0/kJ mol-1 U0/J a (m/(Js)) lifet(s) lifet (ps) U0/a0 (J/m) U0/a0(cm-1/nm)

0 0.1255 2010 9.58 77267.88211 7065.413855 0.01255 1.26E-11 8.45E+01 1.40E-19 1.19E+23 2.01E-09 2.01E+03 1.1184E-08 56298.11836

1 0.0976 57.2 9.775 78840.66259 5492.633373 0.00976 9.76E-12 6.57E+01 1.09E-19 9.25E+22 5.72E-11 5.72E+01 1.1179E-08 56276.98128

2 0.0713 3.1 9.959 80324.72212 4008.573842 0.00713 7.13E-12 4.80E+01 7.96E-20 6.76E+22 3.10E-12 3.10E+00 1.1168E-08 56221.23201

3 10.14 81784.58503 2548.710934 3.05E+01 5.06E-20 :is constant ca. constant

HBr, v=3 10.456 84333.29596 average: 1.1177E-08 56265.44389

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

HBr:

E V

v´=3v´=3v´=2

v´=1v´=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 =a0

0.0725 =a0

0.0351 =a0

Try for U0 = E(v=n)-E(v) for n = 1-2, v = 0,1i.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) v2228 4334 0

0 2106 10 2

Ebarrier Uo(v´=0)/cm-1 Uo(v´=1)/cm-1 Uo(v´=0)/J U0(v´=1)/J ao(v=0)/m ao(v=0)/A Uo(v´=0)/ao(v=0)(J/m) ao(v=1)/m ao(v=1)/A t(v=1)/s t(v=1)/ps

80167.5 2228 0 4.43E-20 0.00E+00 1.80E-11 1.80E-01 2.45E-09 0.00E+00 0.00E+00 1.50E-14 1.50E-02

80439.5 2500 272 4.97E-20 5.40E-21 1.70E-11 1.70E-01 2.92E-09 1.85E-12 1.85E-02 1.90E-14 1.90E-02

80639.5 2700 472 5.36E-20 9.38E-21 1.64E-11 1.64E-01 3.27E-09 2.86E-12 2.86E-02 2.42E-14 2.42E-02

80839.5 2900 672 5.76E-20 1.33E-20 1.58E-11 1.58E-01 3.64E-09 3.66E-12 3.66E-02 3.10E-14 3.10E-02

81039.5 3100 872 6.16E-20 1.73E-20 1.53E-11 1.53E-01 4.03E-09 4.30E-12 4.30E-02 3.96E-14 3.96E-02

81239.5 3300 1072 6.56E-20 2.13E-20 1.48E-11 1.48E-01 4.42E-09 4.82E-12 4.82E-02 5.01E-14 5.01E-02

81439.5 3500 1272 6.95E-20 2.53E-20 1.44E-11 1.44E-01 4.83E-09 5.23E-12 5.23E-02 6.24E-14 6.24E-02

81639.5 3700 1472 7.35E-20 2.92E-20 1.40E-11 1.40E-01 5.25E-09 5.57E-12 5.57E-02 7.68E-14 7.68E-02

81839.5 3900 1672 7.75E-20 3.32E-20 1.36E-11 1.36E-01 5.68E-09 5.85E-12 5.85E-02 9.32E-14 9.32E-02

82039.5 4100 1872 8.14E-20 3.72E-20 1.33E-11 1.33E-01 6.12E-09 6.07E-12 6.07E-02 1.12E-13 1.12E-01

82239.5 4300 2072 8.54E-20 4.12E-20 1.30E-11 1.30E-01 6.58E-09 6.26E-12 6.26E-02 1.32E-13 1.32E-01

82273.5 4334 2106 8.61E-20 4.18E-20 1.29E-11 1.29E-01 6.66E-09 6.29E-12 6.29E-02 1.36E-13 1.36E-01

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 ):

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

NB! According to Long (http://notendur.hi.is/agust/rannsoknir/rempi/hbr/June11/New states summary-290611jl.ppt )Lifetime for E(v´=0) 6.491598 psLifetime for E(v´=1) 2.31441 to 1.058539 ps

Lets try calculations for lifetime E(v´=0 )= 6.5 ps

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-1 Uo(v´=1)/cm-1 Uo(v´=0)/J U0(v´=1)/J ao(v=0)/m ao(v=0)/A Uo(v´=0)/ao(v=0)(J/m) ao(v=1)/m ao(v=1)/A t(v=1)/s t(v=1)/ps

80167.5 2228 0 4.43E-20 0.00E+00 1.68E-11 1.68E-01 2.63E-09 0.00E+00 0.00E+00 1.50E-14 1.50E-02

80439.5 2500 272 4.97E-20 5.40E-21 1.59E-11 1.59E-01 3.12E-09 1.73E-12 1.73E-02 1.87E-14 1.87E-02

80639.5 2700 472 5.36E-20 9.38E-21 1.53E-11 1.53E-01 3.51E-09 2.67E-12 2.67E-02 2.34E-14 2.34E-02

80839.5 2900 672 5.76E-20 1.33E-20 1.48E-11 1.48E-01 3.90E-09 3.42E-12 3.42E-02 2.96E-14 2.96E-02

81039.5 3100 872 6.16E-20 1.73E-20 1.43E-11 1.43E-01 4.31E-09 4.02E-12 4.02E-02 3.72E-14 3.72E-02

81239.5 3300 1072 6.56E-20 2.13E-20 1.38E-11 1.38E-01 4.74E-09 4.50E-12 4.50E-02 4.62E-14 4.62E-02

81439.5 3500 1272 6.95E-20 2.53E-20 1.34E-11 1.34E-01 5.17E-09 4.88E-12 4.88E-02 5.68E-14 5.68E-02

81639.5 3700 1472 7.35E-20 2.92E-20 1.31E-11 1.31E-01 5.62E-09 5.20E-12 5.20E-02 6.89E-14 6.89E-02

81839.5 3900 1672 7.75E-20 3.32E-20 1.27E-11 1.27E-01 6.09E-09 5.46E-12 5.46E-02 8.26E-14 8.26E-02

82039.5 4100 1872 8.14E-20 3.72E-20 1.24E-11 1.24E-01 6.56E-09 5.67E-12 5.67E-02 9.77E-14 9.77E-02

82239.5 4300 2072 8.54E-20 4.12E-20 1.21E-11 1.21E-01 7.04E-09 5.84E-12 5.84E-02 1.14E-13 1.14E-01

82273.5 4334 2106 8.61E-20 4.18E-20 1.21E-11 1.21E-01 7.13E-09 5.87E-12 5.87E-02 1.17E-13 1.17E-01

2200

2150

2100

2050

2000

1950

1900

4.03.53.02.52.01.51.0

Our paper, ´98 (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 0.5065306we(E, D81Br) 1664.973512cm-1wexe(E,D81Br) 29.52060336cm-1

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

agust,heima,....June11/PXP-141111ak.pxp; Gr0, Lay0

excitations according to Castlemanna:

l / nm E(exc.) 2*E(exc.) l low l high E high E low E high-E low Et high Et low

256.1nm 39047.24717 78094.49434 264.1 248.1 40306.33 37864.45 2441.882808 79315.44 76873.55

255.3nm 39169.60439 78339.20877 263.3 247.3 40436.72 37979.49 2457.225464 79567.82 77110.6

254.7nm 39261.87672 78523.75344 262.7 246.7 40535.06 38066.24 2468.82758 79758.17 77289.34

2455.978617

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

a: http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf

88

86

84

82

80

78

76

74

x103

54321

256.7255.3

254.7 nm

256.7255.3

254.7 nm

Ours

Castlemann´s

H81BrE-state

D81BrE-state

ExcitationsAccording toCastlemann

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

Comments:

• excitations for H81Br are clearly to v´= 0

• Excitations to D81Br are also primarely to v´= 0 but because of linewidth of laser beamthere 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 NISTa

- I evaluate e and e xe for DBr from the corresponding values for H81Br by the relationshipe(2) = e (1)* and exe (2) = exe (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 Castlemannsuggests (http://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp112-4644-00.pdf ))

)2(

)1(

a: http://webbook.nist.gov/chemistry/form-ser.html.en-us.en

88

86

84

82

80

78

76

74

x103

54321

256.7255.3

254.7 nm

256.7255.3

254.7 nm

Ours

Castlemann´s

H81BrE-state

D81BrE-state

ExcitationsAccording toCastlemann

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

714.01155

825