Dipole and quadrupole (hyper)polarizability for the asymmetric stretching of carbon dioxide: Improved agreement between theory and experiment

Haskopoulos, Anastasios; Maroulis, George

doi:10.1016/j.cplett.2005.10.023

Cited by 33 publications

(27 citation statements)

References 26 publications

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“…31 The denominator factor u LR (R e , θ ) is the same function evaluated at R e = R e (θ ). The other coefficients for excited states are fixed by C 0,υ 3 =1 6 and the ratio C n,υ 3 =0 λ /C 0,υ 3 =0 6 at the ground state of CO 2 .…”

Section: A Potential Energy Surfacementioning

confidence: 99%

Finite temperature path integral Monte Carlo simulations of structural and dynamical properties of ArN−CO2 clusters

Wang¹,

Xie²

2012

The Journal of Chemical Physics

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We report finite temperature quantum mechanical simulations of structural and dynamical properties of Ar(N)-CO(2) clusters using a path integral Monte Carlo algorithm. The simulations are based on a newly developed analytical Ar-CO(2) interaction potential obtained by fitting ab initio results to an anisotropic two-dimensional Morse/Long-range function. The calculated distributions of argon atoms around the CO(2) molecule in Ar(N)-CO(2) clusters with different sizes are consistent to the previous studies of the configurations of the clusters. A first-order perturbation theory is used to quantitatively predict the CO(2) vibrational frequency shift in different clusters. The first-solvation shell is completed at N = 17. Interestingly, our simulations for larger Ar(N)-CO(2) clusters showed several different structures of the argon shell around the doped CO(2) molecule. The observed two distinct peaks (2338.8 and 2344.5 cm(-1)) in the υ(3) band of CO(2) may be due to the different arrangements of argon atoms around the dopant molecule.

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Section: A Potential Energy Surfacementioning

confidence: 99%

Finite temperature path integral Monte Carlo simulations of structural and dynamical properties of ArN−CO2 clusters

Wang¹,

Xie²

2012

The Journal of Chemical Physics

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“…Without entering into further detail on this issue, it is worthwhile noting that this value was found to be in excellent agreement with refined calculations for the isotropic spectrum, but also to match, in order of magnitude, the result reported in the sole prior study of this overtone. To this end, intermode coupling, involving the two stretching vibrations ν 1 and ν 3 , and anharmonicity effects (electro-optical and mechanical) had to be incorporated, along with quality ab initio data 25,26 for the polarizability anisotropy derivatives. 24 In Secs.…”

Section: B Symmetriesmentioning

confidence: 99%

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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“…This surface is usually expressed as a Taylor series on the vibrational coordinates. The polarizability derivatives can be determined from ab initio calculations [18,19] or, more frequently, empirical values can be obtained from a fit to experimental transition moments [6,20].…”

Section: The Calculated Raman Spectrummentioning

confidence: 99%

A study of the Raman spectrum of CO2 using an algebraic approach

Sánchez-Castellanos

Lemus

Carvajal

et al. 2012

Chemical Physics Letters

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Dipole and quadrupole (hyper)polarizability for the asymmetric stretching of carbon dioxide: Improved agreement between theory and experiment

Cited by 33 publications

References 26 publications

Finite temperature path integral Monte Carlo simulations of structural and dynamical properties of ArN−CO2 clusters

Finite temperature path integral Monte Carlo simulations of structural and dynamical properties of ArN−CO2 clusters

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

A study of the Raman spectrum of CO2 using an algebraic approach

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