Temperature dependent ultraviolet‐visible absorption cross sections of N2O and N2O4: Low‐temperature measurements of the equilibrium constant for 2NO2 ⇌ N2O4

Harwood, Matthew H.; Jones, R. L.

doi:10.1029/94jd01635

Cited by 87 publications

(60 citation statements)

References 13 publications

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“…Data from Schneider et al (1987) show large discrepancies in the wavelength scale. Absolute cross-sections of Harwood and Jones (1994) are systematically 5% lower, and the differential cross-sections are 18% higher.…”

Section: Discussionmentioning

confidence: 98%

“…Comparison with published measurements NO 2 absorption cross-sections will be compared below with the data from Schneider et al(1987), Johnston and Graham (1974), Harwood and Jones(1994), and Mérienne et al (1995), taking into account the conversion of wavelengths to wavenumbers and the correction of wavelengths from air to vacuum when necessary. Figure 3 shows the absolute absorption cross-sections of NO 2 from the four groups of authors in the spectral region from 415 and 465 nm.…”

Section: Error Evaluationmentioning

confidence: 99%

“…Davidson et al(1988) investigated the dependence of the NO 2 cross-sections on temperature and the influence of this dependence on the determination of the photolysis rate of NO 2 in the atmosphere. Harwood and Jones (1994) studied the temperature dependence of the ultraviolet-visible absorption cross section of NO 2 . The cross sections of N 2 O 4 .…”

Section: Introductionmentioning

confidence: 99%

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Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

et al. 1996

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New laboratory measurement of NO 2 absorption cross-sections were performed using a Fourier transform spectrometer at 2 and 16 cm -1 ( 0.03 and 0.26 nm at 400 nm) in the visible range (380-830 nm) and at room temperature. The use of a Fourier transform spectrometer leads to a very accurate wavenumber scale (0.005 cm -1 , 8x10-5 nm at 400 nm). The uncertainty on the new measurements is better than 4%. Absolute and differential cross-sections are compared with published data, giving an agreement ranging from 2% to 5% for the absolute values. The discrepancies in the differential cross-section can however reach 18%. The influence of the cross-sections on the ground-based measurement of the stratospheric NO 2 total amount is also investigated.

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Section: Discussionmentioning

confidence: 98%

Section: Error Evaluationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

et al. 1996

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“…The absorption cross-sections for NO 2 are 1.44 × 10 −19 cm 2 /molec (0.35 Mm −1 /ppb at 1 atm and 273 K) and 4.84 × 10 −19 cm 2 /molec (1.19 Mm −1 /ppb at 1 atm and 273 K) for 355 nm and 532 nm, respectively (Harwood and Jones 1994). NO 2 has highly structured absorption throughout the visible spectrum with cross-sections and FIG.…”

Section: Gas Phase Absorptionmentioning

confidence: 99%

Design and Application of a Pulsed Cavity Ring-Down Aerosol Extinction Spectrometer for Field Measurements

Baynard

Lovejoy

Pettersson

et al. 2007

Aerosol Science and Technology

104

109

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This paper describes the design and application of a pulsed cavity ring-down aerosol extinction spectrometer (CRD-AES) for insitu atmospheric measurement of the aerosol extinction coefficient and its relative humidity dependence. This CRD-AES measures the aerosol extinction coefficient (σ ep ) at 355 nm, 532 nm, 683 nm, and 1064 nm with a minimal size dependent bias for particles with diameter less than 10 μm. The σ ep at 532 nm is measured with an accuracy of 1% when extinction is ≥10 Mm −1 . The precision is limited by statistical fluctuations within the small optical volume and the time resolution of extinction at 2% uncertainty for various air mass types is evaluated. The CRD-AES is configured with two separate cavity ring-down cells for measurement of the extinction coefficient at 532 nm. This allows the determination of the RH dependence of extinction at 532 nm through independent RH control of the sample for each measurement. Gas phase absorption and minimization of potential interferences is also considered.

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“…Both NO 2 and N 2 O 4 absorb light to 400 nm and beyond. 1,30,31 Thus, one possible explanation for the field and laboratory observations may be the formation of complexes between NO 2 and/or N 2 O 4 and HNO 3 or NO 3 À on surfaces. If the NO 2 /N 2 O 4…”

mentioning

confidence: 99%

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

Kamboures

Raff

Miller

et al. 2008

Phys. Chem. Chem. Phys.

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Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO 3 )Á(NO 2 ), (HNO 3 )Á(N 2 O 4 ), (NO 3 À )Á(NO 2 ), and (NO 3 À )Á(N 2 O 4 ). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO 3 À )Á(N 2 O 4 ) possessing binding energy of almost À14 kcal mol À1 . Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm À1 that are attributed to NO 2 complexed to NO 3 À and HNO 3 , respectively. The electronic states of (HNO 3 )Á (N 2 O 4 ) and (NO 3 À )Á(N 2 O 4 ) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO 3 À )Á(N 2 O 4 ) was obtained from UV/vis absorption spectra of N 2 O 4 in concentrated HNO 3 , which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N 2 O 4 dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO 3 )Á(NO 2 ) and (HNO 3 )Á(N 2 O 4 ) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.

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Temperature dependent ultraviolet‐visible absorption cross sections of N₂O and N₂O₄: Low‐temperature measurements of the equilibrium constant for 2NO₂ ⇌ N₂O₄

Cited by 87 publications

References 13 publications

Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

Fourier transform measurement of NO2 absorption cross-section in the visible range at room temperature

Design and Application of a Pulsed Cavity Ring-Down Aerosol Extinction Spectrometer for Field Measurements

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

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