Absorption cross section spectrum for groundstate iodine monoxide IO(v'<-0) --------------------------------------------------------------------------- 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: 25th of May 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 IO_gs_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. Separation also of ground state IO from vibrationally excited IO. The present spectrum contains only absorption bands from IO(v'<-0). - 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 Multichannel Time-resolved Absorption Spectroscopy". Spectro. Chim. Acta A, Vol. 60, pp. 2673-2693 Vertical axis: - Optical density of IO(v'<-0) - Scaled to absorption cross section determined for maximum of IO(4<-0) - Absorption cross section: Determined by conservation of iodine atoms => Independent of previously determined rate coefficients and models of IO formation and consumption. Used only absorption cross sections of I2(500 nm) and I(183.038nm) ATTENTION: Apparent cross section and possition of the maximum depends on resolution. Therefore the present spectrum is scaled to that cross section which is appropriate at the given FWHM of 1.3 nm! sigmaIO(max(4<-0),1.3 nm FWHM) = (2.1 ± 0.2)E-17 cm²/molec (MIntAS corrected: sigmaIO(427,2nm vacuum, 0.12 nm FWHM) = (3.5 ± 0.3)E-17 cm²/molec) ) - pressure dependence: - IO(2<-0): Pressure effect at low pressures, possibly due to chemoluminescence or effect of low resolution, corrected (uncertainty of this correction < 10%). Valid at p > 200 mbar. - remaining spectrum: No pressure dependence detected in the range of 15 to 400 mbar. No unresolved ro-vibrational structures: Spectrum also 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) - Verified by comparison with convoluted and binned CRD spectrum (vac. wavelength) by Newman et al.(1998), J. Chem. Soc., Faraday Trans., Vol. 94, 2681-2688 Deviations between -0.08 nm and +0.07 nm confirming uncertainty of sub-pixel ± 0.1 nm Uncertainty estimate: - Based on individual uncertainty estimate of extracted spectra from individual experimental data set (54 data sets analysed). - 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 [cm²/molec]: sigIO_app (apparent sigma at 1.3nm FWHM!!) - relative uncertainty: reluncert lambdaAir lambdaVac wavenumber sigIO_app reluncert ------------------------------------------------------ 320.26751 320.36007 31214.87672 1.97542E-20 4.79247 320.58073 320.67337 31184.37946 1.68144E-19 0.48138 320.89395 320.98667 31153.94173 8.24121E-21 10.09719 321.20718 321.29997 31123.56326 5.15936E-20 1.69554 321.5204 321.61327 31093.24408 4.6358E-20 1.71065 321.83362 321.92658 31062.98381 -6.30722E-20 -0.94031 322.14684 322.23988 31032.78248 6.96462E-20 0.97957 322.46007 322.55318 31002.63982 6.33072E-20 1.10625 322.77329 322.86648 30972.55556 1.22464E-19 0.65373 323.08651 323.17978 30942.52972 1.51058E-19 0.45932 323.39973 323.49308 30912.56204 2.95262E-20 2.42242 323.71296 323.80639 30882.65226 2.63206E-20 2.7974 324.02618 324.11969 30852.80039 2.08142E-20 3.46036 324.3394 324.43299 30823.00608 1.75273E-20 3.68953 324.65262 324.74629 30793.26935 6.77976E-20 1.29688 324.96585 325.05959 30763.58995 -4.04338E-20 -1.74159 325.27907 325.37289 30733.9676 1.19932E-20 5.53099 325.59229 325.6862 30704.40234 -6.30737E-20 -0.72411 325.90551 325.9995 30674.89381 -1.78684E-20 -2.20271 326.21873 326.3128 30645.44204 6.8567E-20 0.93748 326.53196 326.6261 30616.04677 8.89777E-20 0.67697 326.84518 326.9394 30586.70774 7.36373E-21 7.74767 327.1584 327.25271 30557.42498 5.20155E-20 1.20282 327.47162 327.56601 30528.19823 9.67082E-20 0.64083 327.78485 327.87931 30499.02724 9.91185E-21 4.61823 328.09807 328.19261 30469.91204 2.46273E-20 2.13517 328.41129 328.50591 30440.85228 -9.81701E-21 -6.18295 328.72451 328.81922 30411.84799 2.72637E-20 1.84204 329.03774 329.13252 30382.89892 3.46094E-20 1.54316 329.35096 329.44582 30354.00481 8.89475E-20 0.65608 329.66418 329.75912 30325.1657 1.85211E-20 3.27658 329.9774 330.07242 30296.38124 5.6428E-20 1.15098 330.29063 330.38573 30267.65147 4.34059E-22 141.8593 330.60385 330.69903 30238.97613 2.44501E-20 1.32825 330.91707 331.01233 30210.35498 5.28296E-20 0.9912 331.23029 331.32563 30181.78805 2.51574E-20 2.55036 331.54352 331.63893 30153.27509 7.65975E-20 0.63386 331.85674 331.95224 30124.81587 9.86108E-20 0.69405 332.16996 332.26554 30096.4104 5.19603E-20 1.01973 332.48318 332.57884 30068.05836 5.46984E-20 0.78175 332.7964 332.89214 30039.75977 4.07061E-20 1.203 333.10963 333.20544 30011.5144 -1.42825E-21 -49.16874 333.42285 333.51875 29983.32201 6.90047E-20 0.96681 333.73607 333.83205 29955.18262 3.74004E-20 1.09831 334.04929 334.14535 29927.09591 4.78801E-20 1.01009 334.36252 334.45865 29899.06191 3.24698E-20 1.27986 334.67574 334.77196 29871.08037 7.3112E-20 0.63311 334.98896 335.08526 29843.15108 6.99633E-20 0.93955 335.30218 335.39856 29815.27405 1.47922E-19 0.36785 335.61541 335.71186 29787.44905 1.87138E-19 0.2727 335.92863 336.02517 29759.67584 1.97491E-19 0.27235 336.24185 336.33847 29731.95447 1.52876E-19 0.40084 336.55507 336.65177 29704.28461 2.05758E-19 0.21696 336.8683 336.96507 29676.66628 1.69642E-19 0.3732 337.18152 337.27837 29649.09927 1.54407E-19 0.43625 337.49474 337.59168 29621.58333 1.2154E-19 0.46049 337.80796 337.90498 29594.1185 2.24094E-20 2.92581 338.12119 338.21828 29566.70447 1.93714E-19 0.28395 338.43441 338.53158 29539.34127 2.51293E-19 0.19318 338.74763 338.84489 29512.02867 2.2119E-19 0.2133 339.06085 339.15819 29484.76644 2.86133E-19 0.22042 339.37408 339.47149 29457.55461 2.34233E-19 0.20738 339.6873 339.78479 29430.39297 2.24595E-19 0.24498 340.00052 340.0981 29403.28128 2.64534E-19 0.20086 340.31374 340.4114 29376.21959 3.19841E-19 0.13659 340.62696 340.7247 29349.20757 3.31359E-19 0.14835 340.94019 341.038 29322.24527 3.36441E-19 0.11887 341.25341 341.35131 29295.33246 3.28888E-19 0.1456 341.56663 341.66461 29268.46893 3.4611E-19 0.17827 341.87985 341.97791 29241.6547 3.35729E-19 0.12976 342.19308 342.29121 29214.88947 2.46466E-19 0.18 342.5063 342.60452 29188.17327 2.44514E-19 0.19632 342.81952 342.91782 29161.50589 2.68361E-19 0.20326 343.13274 343.23112 29134.88711 3.42109E-19 0.16244 343.44597 343.54442 29108.31697 3.51036E-19 0.13212 343.75919 343.85773 29081.79524 3.86312E-19 0.16185 344.07241 344.17103 29055.32172 4.01688E-19 0.13859 344.38563 344.48433 29028.89643 4.3992E-19 0.11018 344.69886 344.79764 29002.51908 5.08228E-19 0.09402 345.01208 345.11094 28976.1897 5.12401E-19 0.10954 345.3253 345.42424 28949.90809 5.49884E-19 0.11702 345.63852 345.73754 28923.67402 5.85544E-19 0.0913 345.95174 346.05085 28897.48754 6.29942E-19 0.06768 346.26497 346.36415 28871.34835 5.80137E-19 0.08115 346.57819 346.67745 28845.25648 5.8274E-19 0.10865 346.89141 346.99075 28819.21174 5.74302E-19 0.11475 347.20464 347.30406 28793.21389 6.03234E-19 0.08956 347.51786 347.61736 28767.263 5.27782E-19 0.09492 347.83108 347.93066 28741.35884 5.95929E-19 0.10029 348.1443 348.24397 28715.5012 5.75937E-19 0.10294 348.45752 348.55727 28689.69013 6.23178E-19 0.08396 348.77075 348.87057 28663.92534 7.35167E-19 0.05979 349.08397 349.18387 28638.20686 7.97618E-19 0.05533 349.39719 349.49718 28612.53449 8.12165E-19 0.05892 349.71041 349.81048 28586.90803 8.36411E-19 0.05296 350.02364 350.12378 28561.32751 8.83979E-19 0.0571 350.33686 350.43709 28535.79265 8.78302E-19 0.06641 350.65008 350.75039 28510.30348 9.47894E-19 0.06057 350.9633 351.06369 28484.85981 8.67037E-19 0.05061 351.27653 351.37699 28459.46143 8.73722E-19 0.05109 351.58975 351.6903 28434.10838 9.6871E-19 0.04794 351.90297 352.0036 28408.80046 9.43623E-19 0.0499 352.21619 352.3169 28383.53748 9.36819E-19 0.0465 352.52942 352.6302 28358.31946 9.43102E-19 0.04662 352.84264 352.94351 28333.14613 9.45884E-19 0.0453 353.15586 353.25681 28308.01754 9.96E-19 0.04445 353.46908 353.57011 28282.93347 1.03247E-18 0.05001 353.78231 353.88342 28257.89375 1.10406E-18 0.03545 354.09553 354.19672 28232.89839 1.20279E-18 0.03622 354.40875 354.51002 28207.94714 1.22206E-18 0.04646 354.72197 354.82333 28183.04003 1.21725E-18 0.04458 355.03519 355.13663 28158.17687 1.31975E-18 0.03417 355.34842 355.44993 28133.35745 1.39743E-18 0.03142 355.66164 355.76323 28108.58183 1.36523E-18 0.03313 355.97486 356.07654 28083.8498 1.39099E-18 0.0313 356.28808 356.38984 28059.16118 1.4338E-18 0.03912 356.60131 356.70314 28034.51601 1.41797E-18 0.03533 356.91453 357.01645 28009.91402 1.38021E-18 0.02036 357.22775 357.32975 27985.35524 1.3333E-18 0.03669 357.54097 357.64305 27960.83949 1.36639E-18 0.04236 357.8542 357.95636 27936.36657 1.34698E-18 0.03608 358.16742 358.26966 27911.93654 1.42481E-18 0.03944 358.48064 358.58296 27887.5492 1.53673E-18 0.02753 358.79386 358.89627 27863.20435 1.50902E-18 0.01894 359.10708 359.20957 27838.90205 1.60525E-18 0.03171 359.42031 359.52287 27814.64203 1.68362E-18 0.03087 359.73353 359.83618 27790.42433 1.71748E-18 0.02491 360.04675 360.14948 27766.24876 1.77122E-18 0.02454 360.35997 360.46278 27742.11514 1.82602E-18 0.02045 360.6732 360.77608 27718.02352 1.91713E-18 0.0233 360.98642 361.08939 27693.97362 1.9382E-18 0.02244 361.29964 361.40269 27669.96549 1.92117E-18 0.01941 361.61286 361.71599 27645.99896 1.94459E-18 0.01794 361.92609 362.0293 27622.07383 1.96195E-18 0.02307 362.23931 362.3426 27598.19015 2.00488E-18 0.01909 362.55253 362.6559 27574.34774 2.03608E-18 0.01979 362.86575 362.96921 27550.54641 2.09387E-18 0.02206 363.17898 363.28251 27526.7862 2.03732E-18 0.02263 363.4922 363.59581 27503.06687 2.068E-18 0.01848 363.80542 363.90912 27479.38846 2.15943E-18 0.01615 364.11864 364.22242 27455.75078 2.15972E-18 0.01388 364.43187 364.53572 27432.15366 2.18582E-18 0.01421 364.74509 364.84903 27408.59713 2.22101E-18 0.01721 365.05831 365.16233 27385.08096 2.2551E-18 0.01804 365.37153 365.47563 27361.60517 2.31855E-18 0.01367 365.68476 365.78894 27338.1696 2.39555E-18 0.00741 365.99798 366.10224 27314.77407 2.39836E-18 0.01098 366.3112 366.41554 27291.41862 2.47447E-18 0.01186 366.62442 366.72885 27268.10307 2.53998E-18 0.01192 366.93765 367.04215 27244.82726 2.56522E-18 0.01561 367.25087 367.35545 27221.59122 2.6439E-18 0.01151 367.56409 367.66876 27198.3947 2.72187E-18 0.01116 367.87731 367.98206 27175.23776 2.71202E-18 0.01091 368.19053 368.29536 27152.12021 2.71508E-18 0.01271 368.50376 368.60867 27129.04189 2.75698E-18 0.01338 368.81698 368.92197 27106.00284 2.80736E-18 0.01316 369.1302 369.23528 27083.00282 2.82439E-18 0.01227 369.44342 369.54858 27060.04186 2.84428E-18 0.00907 369.75665 369.86188 27037.11981 2.88571E-18 0.00825 370.06987 370.17519 27014.23648 2.92424E-18 0.01092 370.38309 370.48849 26991.39193 2.91412E-18 0.01121 370.69631 370.80179 26968.58598 2.86856E-18 0.01315 371.00954 371.1151 26945.81846 2.89605E-18 0.01344 371.32276 371.4284 26923.08943 2.95184E-18 0.00911 371.63598 371.7417 26900.39863 2.93467E-18 0.00746 371.9492 372.05501 26877.74612 3.09319E-18 0.00757 372.26243 372.36831 26855.13173 3.11264E-18 0.00784 372.57565 372.68161 26832.55529 3.18067E-18 0.00859 372.88887 372.99492 26810.01684 3.29862E-18 0.00883 373.20209 373.30822 26787.51616 3.38171E-18 0.0095 373.51531 373.62152 26765.05328 3.58457E-18 0.00802 373.82854 373.93483 26742.62805 3.70593E-18 0.00765 374.14176 374.24813 26720.24029 3.81009E-18 0.00749 374.45498 374.56143 26697.89005 3.90067E-18 0.00815 374.7682 374.87474 26675.57717 3.93387E-18 0.00709 375.08143 375.18804 26653.30148 3.90049E-18 0.0083 375.39465 375.50135 26631.06304 3.8255E-18 0.00648 375.70787 375.81465 26608.8616 3.73558E-18 0.0064 376.02109 376.12795 26586.69722 3.62213E-18 0.00795 376.33432 376.44126 26564.56974 3.53017E-18 0.00639 376.64754 376.75456 26542.47898 3.54456E-18 0.00852 376.96076 377.06786 26520.425 3.5464E-18 0.00834 377.27398 377.38117 26498.40757 3.5733E-18 0.00833 377.58721 377.69447 26476.42674 3.63557E-18 0.00716 377.90043 378.00777 26454.48235 3.75271E-18 0.00752 378.21365 378.32108 26432.57423 3.92161E-18 0.00661 378.52687 378.63438 26410.70244 3.99364E-18 0.00745 378.84009 378.94769 26388.86681 4.10344E-18 0.00704 379.15332 379.26099 26367.06718 4.26764E-18 0.00604 379.46654 379.57429 26345.30362 4.47863E-18 0.00641 379.77976 379.8876 26323.57588 4.68609E-18 0.00364 380.09299 380.2009 26301.88402 4.83021E-18 0.00418 380.40621 380.5142 26280.22788 5.01793E-18 0.00587 380.71943 380.82751 26258.6073 5.18716E-18 0.00563 381.03265 381.14081 26237.02234 5.21136E-18 0.0052 381.34588 381.45412 26215.47276 5.17009E-18 0.00455 381.6591 381.76742 26193.95863 4.95908E-18 0.00391 381.97232 382.08072 26172.47977 4.61916E-18 0.00492 382.28554 382.39403 26151.03604 4.27038E-18 0.00525 382.59876 382.70733 26129.62749 3.98806E-18 0.00759 382.91199 383.02063 26108.25397 3.90358E-18 0.00623 383.22521 383.33394 26086.91531 4.02437E-18 0.00532 383.53843 383.64724 26065.61157 4.23029E-18 0.0051 383.85165 383.96055 26044.34253 4.44251E-18 0.00514 384.16488 384.27385 26023.10824 4.73972E-18 0.00341 384.4781 384.58715 26001.90854 5.04164E-18 0.00589 384.79132 384.90046 25980.74329 5.21126E-18 0.00641 385.10454 385.21376 25959.61254 5.3488E-18 0.00417 385.41777 385.52707 25938.51606 5.51548E-18 0.00328 385.73099 385.84037 25917.45391 5.61192E-18 0.00346 386.04421 386.15367 25896.42594 5.64811E-18 0.00272 386.35743 386.46698 25875.43199 5.67291E-18 0.0039 386.67066 386.78028 25854.47212 5.69898E-18 0.00431 386.98388 387.09358 25833.54618 5.71599E-18 0.00413 387.2971 387.40689 25812.65402 5.69937E-18 0.00336 387.61032 387.72019 25791.79569 5.68821E-18 0.00266 387.92354 388.0335 25770.97098 5.62735E-18 0.00312 388.23677 388.3468 25750.17993 5.58169E-18 0.00261 388.54999 388.6601 25729.4224 5.56032E-18 0.00238 388.86321 388.97341 25708.69824 5.56798E-18 0.00472 389.17643 389.28671 25688.00751 5.54918E-18 0.00443 389.48966 389.60002 25667.34999 5.57315E-18 0.00308 389.80288 389.91332 25646.72573 5.57982E-18 0.0031 390.1161 390.22662 25626.13459 5.58196E-18 0.00446 390.42932 390.53993 25605.57642 5.62923E-18 0.00456 390.74255 390.85323 25585.05127 5.66289E-18 0.0034 391.05577 391.16654 25564.55901 5.70848E-18 0.00286 391.36899 391.47984 25544.09947 5.76534E-18 0.0037 391.68221 391.79314 25523.67273 5.79732E-18 0.00483 391.99544 392.10645 25503.27856 5.84431E-18 0.00428 392.30866 392.41975 25482.91702 5.9447E-18 0.00418 392.62188 392.73306 25462.58797 6.04003E-18 0.00499 392.9351 393.04636 25442.29126 6.10808E-18 0.00263 393.24832 393.35966 25422.02694 6.23501E-18 0.00289 393.56155 393.67297 25401.79482 6.37561E-18 0.00321 393.87477 393.98627 25381.59494 6.47642E-18 0.00271 394.18799 394.29958 25361.42716 6.6086E-18 0.00206 394.50122 394.61288 25341.29134 6.71787E-18 0.0019 394.81444 394.92619 25321.18753 6.74115E-18 0.00331 395.12766 395.23949 25301.11559 6.781E-18 0.00365 395.44088 395.55279 25281.07539 6.90129E-18 0.00191 395.7541 395.8661 25261.06697 6.91988E-18 0.00243 396.06733 396.1794 25241.09013 6.90252E-18 0.00341 396.38055 396.49271 25221.14492 6.94656E-18 0.00237 396.69377 396.80601 25201.23121 6.86969E-18 0.00306 397.00699 397.11931 25181.34886 6.80049E-18 0.00347 397.32022 397.43262 25161.49792 6.75411E-18 0.00287 397.63344 397.74592 25141.67819 6.64466E-18 0.00212 397.94666 398.05923 25121.88972 6.54074E-18 0.00249 398.25988 398.37253 25102.13238 6.47086E-18 0.00268 398.57311 398.68584 25082.40602 6.40894E-18 0.00234 398.88633 398.99914 25062.71071 6.36555E-18 0.00182 399.19955 399.31244 25043.0463 6.36146E-18 0.00178 399.51277 399.62575 25023.41267 6.2946E-18 0.00177 399.82599 399.93905 25003.80985 6.23867E-18 0.00273 400.13922 400.25236 24984.23766 6.28522E-18 0.00199 400.45244 400.56566 24964.69616 6.2774E-18 0.00251 400.76566 400.87896 24945.18519 6.39931E-18 0.00153 401.07889 401.19227 24925.70464 6.57168E-18 0.00243 401.39211 401.50557 24906.25455 6.7212E-18 0.00205 401.70533 401.81888 24886.83479 6.96265E-18 0.00148 402.01855 402.13218 24867.44523 7.21676E-18 0.00246 402.33177 402.44549 24848.08592 7.56873E-18 0.00154 402.645 402.75879 24828.75667 7.89978E-18 0.00156 402.95822 403.07209 24809.45752 8.23264E-18 0.00125 403.27144 403.3854 24790.18836 8.53896E-18 0.0016 403.58466 403.6987 24770.94904 8.69685E-18 0.0015 403.89789 404.01201 24751.73963 8.75222E-18 0.00125 404.21111 404.32531 24732.55992 8.67039E-18 0.00308 404.52433 404.63862 24713.40997 8.49302E-18 0.00215 404.83755 404.95192 24694.28966 8.20468E-18 0.00147 405.15078 405.26522 24675.19884 7.80314E-18 0.00168 405.464 405.57853 24656.13759 7.34478E-18 0.00141 405.77722 405.89183 24637.10576 6.91508E-18 0.00121 406.09044 406.20514 24618.10322 6.51556E-18 0.00192 406.40367 406.51844 24599.13004 6.14061E-18 0.00198 406.71689 406.83175 24580.18602 5.827E-18 0.00348 407.03011 407.14505 24561.27121 5.55778E-18 0.0028 407.34333 407.45835 24542.38549 5.41392E-18 0.00318 407.65655 407.77166 24523.52873 5.35937E-18 0.00478 407.96978 408.08496 24504.70099 5.35668E-18 0.0022 408.283 408.39827 24485.90207 5.48472E-18 0.00229 408.59622 408.71157 24467.13204 5.68514E-18 0.003 408.90944 409.02488 24448.39075 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