Absorption cross section spectrum for iodine dioxide OIO -------------------------------------------------------- Recorded and analysed by: Peter Spietz, Juan Carlos Gómez Martín and John P. Burrows The Institute of Environmental Physics and Remote Sensing University of Bremen 28334 Bremen PO-Box 330440 spietz@iup.physik.uni-bremen.de Released: 1st of July 2005 Published: Peter Spietz (2005): "ABSORPTION CROSS SECTIONS FOR IODINE SPECIES OF RELEVANCE TO THE PHOTOLYSIS OF MIXTURES OF I2 AND O3 AND FOR THE ATMOSPHERE", Thesis submitted at 29th of March 2005 to the Committee of the Doctoral Program "Doktor rerum naturalium" at the Department of Physics at the Univeristy of Bremen. Version 2.0 OIO_1.3nm_2005_07_01_ps (vertical scaling and maximum wavelength corrected) (previous: OIO_1.3nm_2005_05_25_ps) Experiment type: - Xenon flash photolysis of mixtures of I2+O3 in bath gases O2 and/or N2. - Flow mode, pressure range 15 to 400 mbar. See below for pressure effects. - 298K - Analysis light source: Xenon arc lamp. - Detection system: - Grating spectrometer Acton Research Company SP500, 500mm focal length, grating 150 grooves/mm. - CCD camera Roper Scientific, 1024 x 1024 pixels, 26µm x 26µm pixel size, operated in time resolved mode. - linear dispersion 0.23nm / pixel - Slit width 50 µm, Field of View filled => - Resolution: 1.3nm FWHM - Reaction vessel: Quarz, 120 cm, multi path optics (White type), mirrors: Al + MgF2, path length from 2400 cm to 3360 cm Analysis: - Absorptions from different absorbers separated by Principal Components Analysis, Independent Components Analysis and Least Squares Techniques. Separated from ground state IO, vibrationally excited IO and I2. - Separation verified: Spectra are free of other absorptions with a remaining uncertainty of estimated 3%. Details: Gómez Martín, J.C., P. Spietz, J. Orphal and J. P. Burrows (2004): "Principal and Independent Component Analysis of Overlapping Spectra in the Context of Mulichannel Time-resolved Absorption Spectroscopy". Spectro. Chim. Acta A, Vol. 60, pp. 2673-2693 Vertical axis: - Optical density of OIO - Scaled to absorption cross section determined at maximum OIO(0,5,1<-0,0,0) at 549.2nm - Absorption cross section: Determined by conservation of iodine atoms => Independent of previously determined rate coefficients and models of IO/OIO formation and consumption. Used only absorption cross sections of I2(500 nm) and I(183.038nm) ATTENTION: Apparent cross section depends on resolution. Therefore the present spectrum is scaled to that cross section which is appropriate at the given FWHM of 1.3 nm! sigma(OIO, 1.3 nm FWHM) = (1.13 +- 0.31)E-17 cm^/molec (MIntAS corrected: sigma(OIO, 0.35 nm FWHM) = (1.3 +- 0.3)E-17 cm^/molec) ) - pressure dependence: - No pressure dependence observed in the range of 15 to 400 mbar. Ashworth et al.[2002]: No unresolved ro-vibrational structures: => Spectrum should also be valid at pressures > 400 mbar. Horizontal axis: - calibrated against Mercury Cadmium line source measurement (wavelength in air). Residuals below 0.1 nm. - Transferred to vaccuum wavelength by Edlen's formula (see Morton (1991) ApJS, 77, 119) Uncertainty estimate: - Based on individual uncertainty estimate of extracted spectra from individual experimental data set. - Resulted from weighted average of individua results and error propagation according to Gauss. Data: - wavelength in air [nm]: lambdaAir - wavelength in vacuum [nm]: lambdaVac - wavenumber [1/cm]: wavenumber - absorption cross section [cm^2/molec]: sigOIO_app (apparent sigma at 1.3nm FWHM!!) - relative uncertainty: reluncert lambdaAir lambdaVac wavenumber sigOIO_app reluncert ------------------------------------------------------ 391.85312 391.9641 25512.54055 2.58437E-19 2.26643E-16 392.16404 392.27509 25492.31438 -5.67354E-19 6.60824E-17 392.47495 392.58609 25472.12019 4.56728E-19 1.99465E-16 392.78586 392.89708 25451.95803 7.41392E-19 -4.40782E-16 393.09677 393.20807 25431.8277 3.23098E-19 3.75851E-15 393.40769 393.51907 25411.72919 -2.3102E-19 1.95639E-14 393.7186 393.83006 25391.66249 4.68095E-20 3.59023E-13 394.02951 394.14106 25371.62738 4.99213E-19 -1.25037E-13 394.34042 394.45205 25351.62393 -3.84253E-19 -6.02673E-13 394.65134 394.76304 25331.65194 -1.13849E-19 7.53777E-12 394.96225 395.07404 25311.71139 1.56664E-19 2.02751E-11 395.27316 395.38503 25291.80227 1.81033E-19 -6.48659E-11 395.58407 395.69602 25271.92438 -1.56128E-19 -2.77714E-10 395.89499 396.00702 25252.07777 2.88548E-19 -5.54136E-10 396.2059 396.31801 25232.26225 -7.58725E-20 -7.76139E-9 396.51681 396.62901 25212.4778 -1.21698E-19 1.77969E-8 396.82772 396.94 25192.72442 -1.00623E-19 -7.90537E-8 397.13864 397.25099 25173.0019 -4.74508E-19 6.14795E-8 397.44955 397.56199 25153.31024 -2.60267E-19 -4.10434E-7 397.76046 397.87298 25133.64942 -3.85856E-19 1.01211E-6 398.07138 398.18397 25114.01925 3.057E-19 4.66236E-6 398.38229 398.49497 25094.41979 3.82417E-19 -1.35778E-5 398.6932 398.80596 25074.85082 -3.93599E-19 -4.79674E-5 399.00411 399.11696 25055.31236 -7.38857E-19 9.27216E-5 399.31503 399.42795 25035.80438 -8.95323E-19 -2.77042E-4 399.62594 399.73894 25016.32669 -9.08516E-19 9.86149E-4 399.93685 400.04994 24996.87935 2.34351E-19 0.01377 400.24776 400.36093 24977.46216 2.25634E-19 -0.05139 400.55868 400.67193 24958.07511 6.87149E-20 2.846 400.86959 400.98292 24938.71819 1.40546E-19 0.08548 401.1805 401.29391 24919.39122 -5.29336E-19 -0.64234 401.49141 401.60491 24900.09424 -8.39857E-19 -0.43758 401.80233 401.9159 24880.82706 -4.62736E-19 -0.02718 402.11324 402.22689 24861.58967 4.91788E-19 0.23248 402.42415 402.53789 24842.38207 5.32251E-20 3.02739 402.73506 402.84888 24823.20406 4.18394E-20 1.15225 403.04598 403.15988 24804.0557 -1.24901E-20 -0.17054 403.35689 403.47087 24784.9368 -1.12388E-20 -7.17506 403.6678 403.78186 24765.84735 -1.01067E-19 -1.02326 403.97872 404.09286 24746.78735 -1.24237E-21 -58.83711 404.28963 404.40385 24727.75659 -1.58273E-19 -0.88056 404.60054 404.71484 24708.75515 -3.23438E-19 -0.11211 404.91145 405.02584 24689.78282 -3.93925E-19 -0.05211 405.22237 405.33683 24670.83961 -3.00841E-19 -0.26044 405.53328 405.64783 24651.9255 -6.01919E-19 -0.75028 405.84419 405.95882 24633.04031 -1.61198E-19 -0.91329 406.1551 406.26982 24614.18403 -4.32553E-19 -0.88335 406.46602 406.58081 24595.35666 -1.52081E-19 -1.08825 406.77693 406.8918 24576.55801 1.58013E-20 10.6365 407.08784 407.2028 24557.78813 -9.22575E-20 -0.10324 407.39875 407.51379 24539.04685 -1.25929E-19 -0.58732 407.70967 407.82479 24520.33414 -1.799E-19 -0.66619 408.02058 408.13578 24501.65001 -3.86057E-20 -1.41274 408.33149 408.44677 24482.99427 -2.11054E-19 -1.40803 408.6424 408.75777 24464.36698 -5.26699E-20 -0.7379 408.95332 409.06876 24445.76796 -6.01455E-20 -2.55263 409.26423 409.37976 24427.19719 -6.04799E-19 -0.09829 409.57514 409.69075 24408.65467 -4.70072E-19 -0.35539 409.88606 410.00174 24390.14022 1.27006E-19 1.80013 410.19697 410.31274 24371.6539 1.42443E-20 9.0831 410.50788 410.62373 24353.19552 -4.06768E-19 -0.35985 410.81879 410.93473 24334.76508 -1.26545E-18 -0.01491 411.12971 411.24572 24316.36258 -9.22519E-19 -0.4543 411.44062 411.55671 24297.98782 -5.75852E-19 -0.63112 411.75153 411.86771 24279.64087 -5.32774E-19 -0.05901 412.06244 412.1787 24261.32155 -6.01792E-21 -45.04585 412.37336 412.4897 24243.02986 -3.62037E-19 -0.3834 412.68427 412.80069 24224.76578 -6.6908E-19 -0.46939 412.99518 413.11168 24206.52914 -1.41064E-19 -1.572 413.30609 413.42268 24188.32 -2.11665E-19 -0.75361 413.61701 413.73367 24170.13817 -4.66173E-19 -0.60345 413.92792 414.04467 24151.98366 -2.57606E-19 -0.34997 414.23883 414.35566 24133.85645 -3.19311E-19 -1.27208 414.54974 414.66665 24115.75638 -3.27774E-20 -7.64654 414.86066 414.97765 24097.68349 -5.71598E-20 -2.26581 415.17157 415.28864 24079.63762 -4.5346E-19 -0.23353 415.48248 415.59964 24061.61875 3.50486E-20 2.77991 415.79339 415.91063 24043.62688 -1.19353E-20 -19.0365 416.10431 416.22162 24025.66185 -8.27385E-20 -1.71487 416.41522 416.53262 24007.72364 -7.71926E-20 -1.70669 416.72613 416.84361 23989.81225 2.94118E-19 0.36076 417.03705 417.15461 23971.92751 -3.93508E-20 -3.586 417.34796 417.4656 23954.06948 3.97668E-20 3.44519 417.65887 417.7766 23936.23797 -9.50612E-20 -1.3984 417.96978 418.08759 23918.433 -3.82638E-20 -4.09162 418.28069 418.39858 23900.65455 -2.40748E-19 -0.51249 418.59161 418.70958 23882.90245 -3.10933E-19 -0.36835 418.90252 419.02057 23865.17676 9.76114E-20 1.46895 419.21343 419.33157 23847.4773 -3.14015E-19 -0.45439 419.52435 419.64256 23829.80408 -1.66183E-19 -0.82299 419.83526 419.95355 23812.15709 5.50925E-20 2.08113 420.14617 420.26455 23794.53616 2.43959E-19 0.55559 420.45708 420.57554 23776.94134 8.44279E-20 1.77783 420.768 420.88654 23759.37247 -3.60882E-19 -0.33942 421.07891 421.19753 23741.82955 -2.35845E-19 -0.37784 421.38982 421.50853 23724.31256 8.84504E-20 0.92625 421.70073 421.81952 23706.82135 3.24988E-19 0.35966 422.01165 422.13051 23689.35597 -1.94937E-19 -0.75659 422.32256 422.44151 23671.91625 1.95955E-19 0.4457 422.63347 422.7525 23654.50219 -5.21904E-20 -1.85524 422.94438 423.0635 23637.11378 1.37578E-19 0.85172 423.2553 423.37449 23619.75086 1.75546E-19 0.60454 423.56621 423.68548 23602.41349 1.79889E-19 0.82037 423.87712 423.99648 23585.1015 1.61011E-19 0.67713 424.18803 424.30747 23567.81488 -2.48742E-19 -0.60556 424.49895 424.61847 23550.55364 2.59752E-20 6.62638 424.80986 424.92946 23533.31761 -1.19461E-19 -0.80529 425.12077 425.24046 23516.10679 8.40498E-20 1.30006 425.43169 425.55145 23498.92118 -1.35339E-20 -8.06749 425.7426 425.86245 23481.76062 -1.65763E-19 -0.60675 426.05351 426.17344 23464.62515 -1.1409E-19 -0.99169 426.36442 426.48443 23447.51462 1.53521E-19 0.54666 426.67534 426.79543 23430.42903 3.41898E-19 0.462 426.98625 427.10642 23413.36837 4.00199E-19 0.36973 427.29716 427.41742 23396.33249 -3.02027E-19 -0.59441 427.60807 427.72841 23379.32143 -1.67614E-19 -1.27017 427.91899 428.03941 23362.33504 4.08366E-19 0.40584 428.2299 428.3504 23345.37331 -4.45291E-21 -37.01963 428.54081 428.66139 23328.43625 1.42205E-19 0.72807 428.85172 428.97239 23311.52369 4.62332E-20 1.64658 429.16264 429.28338 23294.63568 -1.94794E-19 -0.38664 429.47355 429.59438 23277.77208 1.86081E-20 5.1761 429.78446 429.90537 23260.93287 2.02183E-19 0.35679 430.09537 430.21637 23244.11807 -1.36743E-19 -0.94888 430.40629 430.52736 23227.3275 2.67246E-19 0.41707 430.7172 430.83835 23210.56122 2.36357E-19 0.32689 431.02811 431.14935 23193.81908 1.33153E-19 0.78531 431.33903 431.46034 23177.10108 3.66387E-19 0.34984 431.64994 431.77134 23160.40721 2.97112E-19 0.5394 431.96085 432.08233 23143.73731 2.26805E-19 0.57696 432.27176 432.39333 23127.09145 3.49405E-19 0.30427 432.58267 432.70432 23110.46947 5.57277E-19 0.25144 432.89359 433.01532 23093.87136 3.45042E-19 0.29412 433.2045 433.32631 23077.29712 1.40863E-19 0.81052 433.51541 433.6373 23060.74661 6.07257E-19 0.19134 433.82633 433.9483 23044.21982 3.92937E-19 0.31478 434.13724 434.25929 23027.71675 5.09359E-19 0.17146 434.44815 434.57029 23011.23725 4.56115E-19 0.2713 434.75906 434.88128 22994.78137 4.61002E-19 0.35893 435.06998 435.19228 22978.34896 5.7996E-19 0.29944 435.38089 435.50327 22961.94002 7.1305E-19 0.21216 435.6918 435.81427 22945.55455 7.34078E-19 0.18192 436.00271 436.12526 22929.19239 7.12403E-19 0.23016 436.31363 436.43625 22912.85361 4.41132E-19 0.27234 436.62454 436.74725 22896.53804 5.16213E-19 0.22705 436.93545 437.05824 22880.24569 7.76018E-19 0.14704 437.24636 437.36924 22863.97656 3.11221E-19 0.47372 437.55728 437.68023 22847.7305 4.88226E-19 0.25341 437.86819 437.99123 22831.50756 5.33494E-19 0.19428 438.1791 438.30222 22815.30759 5.60438E-19 0.15383 438.49001 438.61322 22799.1306 6.98041E-19 0.14065 438.80093 438.92421 22782.97658 7.43233E-19 0.09866 439.11184 439.23521 22766.84538 5.52043E-19 0.18897 439.42275 439.5462 22750.73706 3.25799E-19 0.44127 439.73366 439.85719 22734.65147 2.94474E-19 0.37548 440.04458 440.16819 22718.58861 2.55007E-19 0.54419 440.35549 440.47918 22702.54848 2.10886E-19 0.76104 440.6664 440.79018 22686.53093 4.58945E-19 0.31359 440.97732 441.10117 22670.53602 2.35324E-19 0.46206 441.28823 441.41217 22654.5636 4.00682E-19 0.29456 441.59914 441.72316 22638.61366 7.85155E-19 0.17805 441.91005 442.03416 22622.68622 8.65575E-19 0.10705 442.22097 442.34515 22606.78113 7.59244E-19 0.15393 442.53188 442.65614 22590.89844 6.63924E-19 0.16737 442.84279 442.96714 22575.03799 6.24952E-19 0.20326 443.1537 443.27813 22559.1998 7.3719E-19 0.12392 443.46462 443.58913 22543.38387 8.91979E-19 0.08853 443.77553 443.90012 22527.59005 1.04148E-18 0.10228 444.08644 444.21112 22511.81834 9.84924E-19 0.13263 444.39735 444.52211 22496.06876 8.6799E-19 0.17738 444.70827 444.83311 22480.34114 8.85429E-19 0.25154 445.01918 445.1441 22464.63555 8.84197E-19 0.30906 445.33009 445.4551 22448.95184 1.09288E-18 0.25713 445.641 445.76609 22433.29001 1.32557E-18 0.20438 445.95192 446.07709 22417.65007 1.02057E-18 0.22108 446.26283 446.38808 22402.03187 8.39062E-19 0.16047 446.57374 446.69907 22386.43547 8.97904E-19 0.15953 446.88466 447.01007 22370.86072 9.77852E-19 0.1664 447.19557 447.32106 22355.30763 7.90614E-19 0.16346 447.50648 447.63206 22339.77619 8.86443E-19 0.1738 447.81739 447.94305 22324.26628 1.18866E-18 0.11229 448.12831 448.25405 22308.77793 9.50936E-19 0.13083 448.43922 448.56504 22293.31101 5.84628E-19 0.18727 448.75013 448.87604 22277.86553 4.25034E-19 0.31163 449.06104 449.18703 22262.44147 4.09225E-20 2.72363 449.37196 449.49803 22247.03872 -1.77799E-19 -0.62821 449.68287 449.80902 22231.65731 1.71626E-19 0.57095 449.99378 450.12002 22216.2971 4.57188E-19 0.2115 450.30469 450.43101 22200.95811 5.86439E-19 0.16561 450.61561 450.742 22185.64033 7.24941E-19 0.12946 450.92652 451.053 22170.34362 9.08251E-19 0.10134 451.23743 451.36399 22155.06805 1.00526E-18 0.12107 451.54834 451.67499 22139.81346 1.09737E-18 0.12119 451.85926 451.98598 22124.57986 1.14403E-18 0.12447 452.17017 452.29698 22109.36726 1.11887E-18 0.10579 452.48108 452.60797 22094.17551 1.16306E-18 0.0928 452.792 452.91897 22079.00463 1.07135E-18 0.12352 453.10291 453.22996 22063.85461 1.01804E-18 0.13257 453.41382 453.54096 22048.72533 1.20316E-18 0.06797 453.72473 453.85195 22033.61683 1.22672E-18 0.09353 454.03564 454.16295 22018.52896 1.13385E-18 0.07494 454.34656 454.47394 22003.46175 1.12717E-18 0.06418 454.65747 454.78494 21988.4152 1.00704E-18 0.09365 454.96838 455.09593 21973.38916 9.40908E-19 0.10704 455.27929 455.40693 21958.38369 7.07966E-19 0.12502 455.59021 455.71792 21943.39865 9.07037E-19 0.11156 455.90112 456.02892 21928.43405 1.04038E-18 0.08994 456.21203 456.33991 21913.48989 1.31171E-18 0.07142 456.52295 456.6509 21898.56604 1.40309E-18 0.06882 456.83386 456.9619 21883.66256 1.17596E-18 0.07724 457.14477 457.27289 21868.77929 1.2659E-18 0.07458 457.45568 457.58389 21853.91626 1.25794E-18 0.06462 457.7666 457.89488 21839.07346 1.16531E-18 0.06564 458.07751 458.20588 21824.25077 1.06202E-18 0.09452 458.38842 458.51687 21809.44823 6.14396E-19 0.16534 458.69933 458.82787 21794.6657 3.50831E-19 0.24727 459.01025 459.13886 21779.90321 3.19727E-19 0.26839 459.32116 459.44986 21765.16074 4.14145E-19 0.21536 459.63207 459.76085 21750.43817 8.27421E-19 0.11271 459.94298 460.07185 21735.73556 8.85063E-19 0.09383 460.2539 460.38284 21721.05276 9.4451E-19 0.12541 460.56481 460.69384 21706.38978 1.63335E-18 0.06251 460.87572 461.00483 21691.74663 1.72856E-18 0.06786 461.18663 461.31583 21677.12318 1.65515E-18 0.05676 461.49755 461.62682 21662.51948 1.58988E-18 0.07215 461.80846 461.93782 21647.9354 1.52492E-18 0.09175 462.11937 462.24881 21633.37094 1.60147E-18 0.07598 462.43029 462.55981 21618.82611 1.5029E-18 0.08612 462.7412 462.8708 21604.30078 1.32704E-18 0.07518 463.05211 463.1818 21589.79495 1.61668E-18 0.04627 463.36302 463.49279 21575.30864 1.69425E-18 0.06405 463.67394 463.80379 21560.84171 1.63474E-18 0.08101 463.98485 464.11478 21546.39421 1.69528E-18 0.06686 464.29576 464.42577 21531.96601 1.5534E-18 0.07935 464.60667 464.73677 21517.55713 1.64858E-18 0.07486 464.91759 465.04776 21503.16756 1.55617E-18 0.06895 465.2285 465.35876 21488.79717 1.46226E-18 0.0642 465.53941 465.66975 21474.44603 1.49969E-18 0.07143 465.85032 465.98075 21460.114 1.45169E-18 0.0712 466.16124 466.29174 21445.80109 1.52411E-18 0.06397 466.47215 466.60274 21431.5073 1.46695E-18 0.05528 466.78306 466.91373 21417.2325 1.28478E-18 0.0741 467.09397 467.22473 21402.97676 1.43761E-18 0.08037 467.40489 467.53572 21388.73993 1.66292E-18 0.05678 467.7158 467.84672 21374.52203 1.7221E-18 0.04904 468.02671 468.15771 21360.32307 1.64089E-18 0.04323 468.33763 468.46871 21346.14291 1.77208E-18 0.04289 468.64854 468.7797 21331.98161 1.90385E-18 0.04236 468.95945 469.0907 21317.83905 1.84112E-18 0.09004 469.27036 469.40169 21303.71522 1.74618E-18 0.16571 469.58128 469.71269 21289.61014 1.64791E-18 0.21951 469.89219 470.02368 21275.52369 1.54615E-18 0.24912 470.2031 470.33468 21261.4559 1.67705E-18 0.17721 470.51401 470.64567 21247.40666 1.56015E-18 0.13423 470.82493 470.95667 21233.37598 1.52545E-18 0.10084 471.13584 471.26766 21219.36386 1.58808E-18 0.06884 471.44675 471.57866 21205.37017 1.73909E-18 0.04718 471.75766 471.88965 21191.39493 1.97162E-18 0.04239 472.06858 472.20065 21177.43815 2.22299E-18 0.03258 472.37949 472.51164 21163.49969 2.5761E-18 0.02649 472.6904 472.82264 21149.57961 2.6783E-18 0.03322 473.00131 473.13363 21135.67778 2.60106E-18 0.03981 473.31223 473.44463 21121.79422 2.49989E-18 0.04424 473.62314 473.75562 21107.92893 2.30698E-18 0.03983 473.93405 474.06662 21094.08179 2.14538E-18 0.02933 474.24496 474.37761 21080.25285 2.13566E-18 0.02779 474.55588 474.68861 21066.44198 1.97996E-18 0.04011 474.86679 474.9996 21052.6492 1.73429E-18 0.03844 475.1777 475.3106 21038.87451 1.82465E-18 0.02691 475.48861 475.62159 21025.11779 1.89332E-18 0.03115 475.79953 475.93259 21011.37909 1.93899E-18 0.02508 476.11044 476.24358 20997.6583 2.07262E-18 0.02888 476.42135 476.55458 20983.95541 2.12203E-18 0.03884 476.73226 476.86557 20970.27043 2.25491E-18 0.0326 477.04318 477.17657 20956.60325 2.23388E-18 0.02793 477.35409 477.48756 20942.95392 2.17749E-18 0.0358 477.665 477.79856 20929.32232 2.13904E-18 0.03685 477.97592 478.10955 20915.70844 1.94188E-18 0.03245 478.28683 478.42055 20902.11231 1.90095E-18 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