Role of intramolecular interactions in Raman spectra of N2 and O2 molecules

Buldakov, Mikhail A.; Cherepanov, Victor N.; Korolev, B. V.; Matrosov, I. I.

doi:10.1016/s0022-2852(02)00012-7

Cited by 39 publications

(9 citation statements)

References 14 publications

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“…Upon using the data values for (ᾱ 1 ) e and (β 1 ) e reported by Buldakov et al, 30 we obtain χ 1 = 1.2 and thus η int ≈ 0.16; with the data of Maroulis, 31 we find χ 1 = 1.1 and thus η int ≈ 0.14. A good example to illustrate this point is the ν 1 transition of N 2 .…”

Section: The Spectral Momentsupporting

confidence: 59%

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized?: The 2ν3 overtone of CO2

Chrysos

Verzhbitskiy

Rachet

et al. 2011

The Journal of Chemical Physics

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Molecular vibrations that are not totally symmetrical give rise to depolarized lines [P. Atkins and J. de Paula, Atkins' Physical Chemistry (Oxford University Press, UK, 2006), p. 464]. But in the case of stretching vibrations in centrosymmetric molecules, the statement has so far not been conclusively verified. It is the purpose of this article to report a rigorous experimental and theoretical analysis of the 2ν(3) band of CO(2)--the first overtone of the asymmetrical stretch vibration. The anisotropic spectrum was extracted and its spectral moment calculated from light-scattering measurements, taken at room temperature and for a wide range of CO(2)-gas densities. Evidence for a near-entirely depolarized Raman band is provided, with integrated depolarization ratio η(int)=6/7.16, closely approaching the upper bound η(max)=6/7. Agreement with theoretical predictions is found, on the basis of quality ab initio data for polarizability properties, provided that electro-optical and mechanical anharmonicity and intermode coupling effects between symmetric ν(1) and antisymmetric ν(3) stretching vibrations are incorporated.

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Section: The Spectral Momentsupporting

confidence: 59%

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized?: The 2ν3 overtone of CO2

Chrysos

Verzhbitskiy

Rachet

et al. 2011

The Journal of Chemical Physics

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“…To calculate the latter, the matrix elements of x k given in Tipping [, ] were used, and the needed Dunham coefficients were taken in Table 1 of Buldakov et al . [].…”

Section: Calculationsmentioning

confidence: 99%

Collision‐induced absorption by N₂ near 2.16 µm: Calculations, model, and consequences for atmospheric remote sensing

2017

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Classical molecular dynamics simulations (CMDS) are used for calculations of the collision‐induced absorption (CIA) by pure N2 in the (2.1–2.2 µm) region of the first overtone band. They lead to reasonable (±15%) agreement with the only two laboratory measurements available, at 97 K and room temperature. Based on these experiment/theory comparisons, empirical corrections are made to the CMDS‐calculated CIA of pure N2 in the 200–300 K temperature range. In addition, the contribution of N2‐O2 collisions is, in the absence of any laboratory measurement, calculated and a simple semiempirical model (the first of its kind) is built in order to predict the CIA of N2 under Earth atmosphere conditions. This is successfully validated by comparisons with ground‐based atmospheric transmission spectra in the 2.1–2.2 µm region.

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“…where m is a rotational line number; in our case, m takes the values −2J − 3 for J = −2, and 2J + 3 for J = 2. 25 Except molecular hydrogen, 26 the Herman-Wallis corrections have only a very minor effect on the transitions J = 0, so F υ υ = 1. This is true irrespective of whether it is the anisotropic or the isotropic spectrum that is concerned by the branch Q.…”

Section: B the Strengthsmentioning

confidence: 99%

The depolarized Raman 2ν3 overtone of CO2: A line-mixing shape analysis

Verzhbitskiy

Kouzov

Rachet

et al. 2011

The Journal of Chemical Physics

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In a recent article we showed that the 2ν(3) transition of CO(2) gives rise to a Raman spectrum that is almost entirely depolarized [M. Chrysos, I. A. Verzhbitskiy, F. Rachet, and A. P. Kouzov, J. Chem. Phys. 134, 044318 (2011)]. In the present article, we go further forward in the study of this overtone by reporting a first-principles shape analysis of its depolarized spectrum at room temperature. As a first step in our analysis, a model assuming isolated Lorentzian line shapes was applied, which at low gas densities turns out to be sufficient for qualitative conclusions. As the next step, a sophisticated approach was developed on the basis of the extended strong-collision model in order to properly account for the heavy line mixing between rotational lines. Whereas a marked deviation between model and measured spectra was observed upon application of the simpler model, striking agreement even at the highest CO(2) density was found on applying the sophisticated one. Accurate calculated data were used for the rotational line broadening coefficients without resort to arbitrary parameters. Values for the vibrational shift scaling linearly with the density of the gas are given.

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Role of intramolecular interactions in Raman spectra of N2 and O2 molecules

Cited by 39 publications

References 14 publications

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized?: The 2ν3 overtone of CO2

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized?: The 2ν3 overtone of CO2

Collision‐induced absorption by N₂ near 2.16 µm: Calculations, model, and consequences for atmospheric remote sensing

The depolarized Raman 2ν3 overtone of CO2: A line-mixing shape analysis

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Role of intramolecular interactions in Raman spectra of N2 and O2 molecules

Cited by 39 publications

References 14 publications

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized?: The 2ν3 overtone of CO2

Are asymmetric stretch Raman spectra by centrosymmetric molecules depolarized?: The 2ν3 overtone of CO2

Collision‐induced absorption by N2 near 2.16 µm: Calculations, model, and consequences for atmospheric remote sensing

The depolarized Raman 2ν3 overtone of CO2: A line-mixing shape analysis

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Collision‐induced absorption by N₂ near 2.16 µm: Calculations, model, and consequences for atmospheric remote sensing