The rotational and rotation‐vibrational Raman spectra of 14N2, 14N15N and 15N2

Bendtsen, Jørgen

doi:10.1002/jrs.1250020204

Cited by 207 publications

(89 citation statements)

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“…We are unaware of a discussion of vibrational Raman scattering by gas-phase molecules for tropospheric absorbers measured by MAX-DOAS, where in addition to N 2 and O 2 also H 2 O could play a role. The Stokes Raman vibrational scattering cross sections of N 2 , and O 2 are about 50, and 100 times weaker than their rotational Raman scattering homologues, yet they are 15 times stronger for H 2 O (Fenner et al, 1973;Bendtsen, 1974;Penney and Lapp, 1976;Avila et al, 1999Avila et al, , 2003Brodersen and Bendtsen, 2003). In the tropical marine boundary layer O 2 and H 2 O add ∼30 % and <15 % relative to N 2 to the vibrational Raman scattering intensity.…”

Section: Discussion Of Rms Limitations Of Field Measurementsmentioning

confidence: 93%

The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

et al. 2011

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Abstract. We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO 2 ) and the oxygen dimer (O 4 ) in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS of ∼6 × 10 −6 from solar stray light noise tests using high photon count spectra (compatible within a factor of two with photon shot noise).Laboratory tests revealed two critical instrument properties that, in practice, can limit the RMS: (1) detector non-linearity noise, RMS NLin , and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMS FWHM . The nonlinearity of our detector is low (∼10 −2 ) yet -unless actively controlled -is sufficiently large to create RMS NLin of up to 2 × 10 −4 . The optical resolution is sensitive to temperature changes (0.03 detector pixels • C −1 at 334 nm), and temperature variations of 0.1 • C can cause RMS FWHM of ∼1 × 10 −4 . Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. With an integration time of 60 s Correspondence to: R. Volkamer (rainer.volkamer@colorado.edu) the instrument can reach RMS noise of 3 × 10 −5 , and typical RMS in field measurements ranged from 6 × 10 −5 to 1.4 × 10 −4 .The CU GMAX-DOAS was set up at a coastal site near Pensacola, Florida, where we detected BrO, IO and CHO-CHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities (average of data above the detection limit), VCDs, of ∼2 × 10 13 molec cm −2 , 8 × 10 12 molec cm −2 and 4 × 10 14 molec cm −2 , respectively. HCHO and NO 2 were also detected with typical MBL VCDs of 1 × 10 16 and 3 × 10 15 molec cm −2 . These are the first measurements of BrO, IO and CHOCHO over the Gulf of Mexico. The atmospheric implications of these observations for elevated mercury wet deposition rates in this area are briefly discussed. The CU GMAX-DOAS has great potential to investigate RMS-limited problems, like the abundance and variability of trace gases in the MBL and possibly the free troposphere (FT).

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Section: Discussion Of Rms Limitations Of Field Measurementsmentioning

confidence: 93%

The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

et al. 2011

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“…The experimental resolution of these line pairs allows the determination of the D͑v =0͒ fine-structure splitting. The D − X͑0,0͒ rotational-branch transition energies determined from all spectra, together with the corresponding D͑v =0͒ rotational term values calculated using X-state terms derived from the spectroscopic parameters of Bendtsen, 26 are summarized in Table I 6 except that the present D v value is not determined well since only low-N levels have been studied. However, this is the first time that the D − X transition has been observed optically and the present data give the first absolute band origin for D − X͑0,0͒ in 14 N 2 .…”

Section: Resultsmentioning

confidence: 99%

Structure and predissociation of the 3pσuD Σ3u+ Rydberg state of N2: First extreme-ultraviolet and new near-infrared observations, with coupled-channels analysis

Lewis

Baldwin

Heays

et al. 2008

The Journal of Chemical Physics

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The 3p u D 3 ⌺ u + Rydberg state of N 2 is studied experimentally using two high-resolution spectroscopic techniques. First, the forbidden D 3 ⌺ u + − X 1 ⌺ g + transition is observed for the first time via the ͑0,0͒ band of 14 N 2 and the ͑1,0͒ band of 15 N 2 , using 1 extreme-ultraviolet +1 ultraviolet two-photon-ionization laser spectroscopy. Second, the Rydberg-Rydberg transition D 3 ⌺ u + − E 3 ⌺ g + is studied using near-infrared diode-laser photoabsorption spectroscopy, thus extending the previous measurements of Kanamori et al. ͓J. Chem. Phys. 95, 80 ͑1991͔͒, to higher transition energies, and thereby revealing the ͑2,2͒ and ͑3,3͒ bands. The combined results show that the D͑v =0-3͒ levels exhibit rapidly increasing rotational predissociation as v increases, spanning nearly four orders of magnitude. The D-state level structure and rotational predissociation signature are explained by means of a coupled-channels model which considers the electrostatically coupled 3 ⌸ u Rydberg-valence manifold, together with a pure-precession L-uncoupling rotational interaction between the 3p u D 3 ⌺ u + and 3p u G 3 ⌸ u Rydberg p-complex components.

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“…1 and the rotational analysis were carried out using the published line positions ͑low NЈ values͒ of Hanisco and Kummel, 14 by assigning the measured rotational lines in an iterative fashion. By using the published ground state rotational constants, 40 the excited state rotational constants were determined by fitting all the rotational energies of the Q-branch transitions to the following expression:…”

Section: Resultsmentioning

confidence: 99%

Rotationally resolved photoelectron spectroscopy of hot N2 formed in the photofragmentation of N2O

Rijs

Backus

Lange

et al. 2001

The Journal of Chemical Physics

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Articles you may be interested inThe photoionization dynamics of rotationally hot molecular nitrogen are studied employing resonance enhanced multiphoton ionization in combination with photoelectron spectroscopy. Photodissociation of N 2 O at ϳ203 nm results in highly rotationally excited N 2 fragments in X 1 ͚ g ϩ (NЉ,vЉϭ0,1) states and O atoms in the excited 1 D 2 state. Photoelectron detection of the rotationally hot N 2 states is performed by a two-photon excitation to the lowest aЉ 1 ͚ g ϩ Rydberg state followed by one-photon ionization. The large number of observed rotational levels, from NЈ ϭ49 up to NЈϭ94, results in improved rotational parameters for aЉ 1 ͚ g ϩ (vЈϭ0). In addition, experimental and theoretical rotationally resolved photoelectron spectra of the aЉ 1 ͚ g ϩ (vЈ ϭ0,1;NЈ) state are presented. In these spectra only ⌬NϭN ϩ ϪNЈϭeven transitions are observed, with a dominant ⌬Nϭ0 peak and rather weak ⌬NϭϮ2 peaks. The one-photon ionization is dominated by ejection of electrons in p and f partial waves. The agreement between experimental and calculated spectra is excellent.

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The rotational and rotation‐vibrational Raman spectra of ¹⁴N₂, ¹⁴N¹⁵N and ¹⁵N₂

Cited by 207 publications

References 16 publications

The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

Structure and predissociation of the 3pσuD Σ3u+ Rydberg state of N2: First extreme-ultraviolet and new near-infrared observations, with coupled-channels analysis

Rotationally resolved photoelectron spectroscopy of hot N2 formed in the photofragmentation of N2O

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