Quantum-interference effects in the o1Πu(v=1)∼b1Πu(v=9) Rydberg–valence complex of molecular nitrogen

Vieitez, M.O.; Ivanov, T.I.; Sprengers, J. P.; Langey, C. A. de; Ubachs, Wim; Lewis, B. R.; Stark, G.

doi:10.1080/00268970701291750

Cited by 12 publications

(20 citation statements)

References 31 publications

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“…[29][30][31] and only a few scattered observations of 14 N 15 N appearing in natural abundance (0.74%). 14,22,30,32 This is despite the latter being of particular importance to studies of isotopic fractionation in planetary atmospheres. 33 Information on f values and predissociation rates of the secondary isotopomers is very limited but comparison with common bands of 14 N 2 shows large differences in the observed energy-level perturbations and predissociation rates.…”

Section: Introductionmentioning

confidence: 99%

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

Heays¹,

Dickenson²,

Salumbides³

et al. 2011

The Journal of Chemical Physics

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The first comprehensive high-resolution photoabsorption spectrum of 14 N 15 N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000-109 000 cm −1 (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N 2 that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schrödinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.

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Section: Introductionmentioning

confidence: 99%

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

Heays¹,

Dickenson²,

Salumbides³

et al. 2011

The Journal of Chemical Physics

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“…However, a recent analysis of the FUSE spectra by Bishop et al [2007] has found bright c 0 4 1 S u + (0) À X 1 S g + (6 -9) emission. This strength has been explained by Liu et al [2008] as the result of the homogeneous coupling of c 0 1), which has a crossing rotational term series and much larger Franck-Condon factors for transitions to the vibrationally excited ground state. In fact, because of this coupling and the overlap of emission lines, the c 0 Bishop et al [2007] might more appropriately be labeled as the coupled c 0 et al [2008] have recently performed a joint experimental and theoretical study of the c 0 4 1 S u + (0) À X 1 S g + band system and obtained consistent oscillator strengths and predissociation rates.…”

Section: Introductionmentioning

confidence: 80%

“…The significantly reduced observed emission rate of c 0 4 1 S u + (0) $ b 0 1 S u + (1) À X 1 S g + (0) and distortion of the c 0 4 1 S u + (0) $ b 0 1 S u + (1) À X 1 S g + (0 -2) band shapes have also been explained qualitatively in terms of multiple scattering, predissociation, and radiative escape. 1 S u + (0) AND b 01 S u + (1) À X 1 S g + DAYGLOW EMISSION 1 S u + (0) AND b 01 S u + (1) À X 1 S g + DAYGLOW EMISSION…”

Section: Discussionmentioning

confidence: 99%

“…Stevens et al [1994] attributed this weakness in dayglow emission to multiple scattering and predissociation of the c 0 4 1 S u + (0) level. They also found the c 0 1) band emission, which is the second-strongest emission channel from c 0 4 1 S u + (0) in the absence of multiple scattering, to be attenuated by the nearly coincident and highly predissociative b 1 P u (2) À X 1 S g + (0) transition. Because the (diabatic) Franck-Condon factors for the c 0 Whang et al, 1996], it was expected that the dayglow emission to v i > 1 levels would be very weak.…”

Section: Introductionmentioning

confidence: 92%

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Analysis of terrestrial thermospheric N₂c′₄¹Σ_u⁺(0) ∼ b′ ¹Σ_u⁺(1) − X¹Σ_g⁺ dayglow emission observed by the Far Ultraviolet Spectroscopic Explorer

Liu¹,

Heays²,

Shemansky³

et al. 2009

J. Geophys. Res.

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Terrestrial thermospheric dayglow emission from the coupled and overlapping c′41Σu+(0) and b′ 1Σu+(1) levels of molecular nitrogen, observed by the Far Ultraviolet Spectroscopic Explorer, is analyzed with the aid of a coupled channels quantum mechanical model of N2 spectroscopy and predissociation dynamics. Model emission spectra for the mixed c′41Σu+(0) ∼ b′ 1Σu+(1) − X1Σg+(vi = 2, 6–9) transitions, calculated for the case of excitation by photoelectron impact, are in excellent agreement with the observations. While the principal excitation mechanism for N2 in the thermosphere is photoelectron impact, evidence is also found in other transitions of resonant fluorescence, induced by lines in the solar atomic hydrogen Lyman series, atomic oxygen transitions, and other N2 bands. The observed emission rate of the c′41Σu+(0) ∼ b′ 1Σu+(1) − X1Σg+(0) band is ∼1% of that inferred from the emission rates to X1Σg+(vi > 2) levels. A qualitative explanation is given for the drastically reduced intensity and band shape distortion observed in the c′41Σu+(0) − X1Σg+(0) emission band. Estimates of the total electron excitation rates for the nominal b′ 1Σu+(1) and c′41Σu+(0) levels are determined from the spectrum by extrapolating the model through regions containing unmeasured and/or resonantly absorbed bands.

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“…By analogy with the vibronic case, such perturbations can cause rotational quantum-interference effects, leading, in some cases, to complete damping of intensity. 4 Second, the singlet states show predissociation behavior that is also erratic. Four decades ago, Carroll and Collins 5 noted that, of the vibrational levels of the b 1 ⌸ u valence state, only v = 1, 5, and 6 could be observed in emission.…”

Section: Introductionmentioning

confidence: 99%

Interactions of the 3pπucΠu1(v=2) Rydberg-complex member in isotopic N2

Vieitez

Ivanov

Lange

et al. 2008

The Journal of Chemical Physics

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The 3ppi u c1Pi u-X 1Sigmag+(2,0) Rydberg and b' 1Sigmau+-X 1Sigmag+(7,0) valence transitions of 14N2, 14N15N, and 15N2 are studied using laser-based 1 extreme ultraviolet (XUV)+1' UV two-photon-ionization spectroscopy, supplemented by synchrotron-based hotoabsorption measurements in the case of 14N2. For each isotopomer, effective rotational interactions between the c(v=2) and b'(v=7) levels are found to cause strong Lambda-doubling in c(v=2) and dramatic P/R-branch intensity anomalies in the b'-X(7,0) band due to the effects of quantum interference. Local perturbations in energy and predissociation line width for the c(v=2) Rydberg level are observed and attributed to a spin-orbit interaction with the crossing, short-lived C 3Pi u(v=17) valence level.

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Quantum-interference effects in the o¹Π_u(v=1)∼b¹Π_u(v=9) Rydberg–valence complex of molecular nitrogen

Cited by 12 publications

References 31 publications

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

Analysis of terrestrial thermospheric N₂c′₄¹Σ_u⁺(0) ∼ b′ ¹Σ_u⁺(1) − X¹Σ_g⁺ dayglow emission observed by the Far Ultraviolet Spectroscopic Explorer

Interactions of the 3pπucΠu1(v=2) Rydberg-complex member in isotopic N2

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Quantum-interference effects in the o1Πu(v=1)∼b1Πu(v=9) Rydberg–valence complex of molecular nitrogen

Cited by 12 publications

References 31 publications

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

Analysis of terrestrial thermospheric N2c′41Σu+(0) ∼ b′ 1Σu+(1) − X1Σg+ dayglow emission observed by the Far Ultraviolet Spectroscopic Explorer

Interactions of the 3pπucΠu1(v=2) Rydberg-complex member in isotopic N2

Contact Info

Product

Resources

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Quantum-interference effects in the o¹Π_u(v=1)∼b¹Π_u(v=9) Rydberg–valence complex of molecular nitrogen

Analysis of terrestrial thermospheric N₂c′₄¹Σ_u⁺(0) ∼ b′ ¹Σ_u⁺(1) − X¹Σ_g⁺ dayglow emission observed by the Far Ultraviolet Spectroscopic Explorer