Multipolar Polarizabilities from Interaction-induced Raman Scattering

Bancewicz, T.; Duff, Y. Le; Godet, Jean‐Luc

doi:10.1002/0471231479.ch6

Cited by 22 publications

(17 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…35 This is almost invariably the case for the quadrupole polarizabilities. Although for certain classes of molecules it might be possible to deduce values for some of these properties, 36 theory remains in general the only source of data. Our calculations rely essentially on the finite-field method.…”

Section: Introductionmentioning

confidence: 99%

Ab initio determination of the electric multipole moments and static (hyper)polarizability of HCCX, X = F, Cl, Br, and I

Maroulis

2003

J Comput Chem

View full text Add to dashboard Cite

We report electric multipole moments and (hyper)polarizabilities for the haloethynes HCCX, X = F, Cl, Br, and I. The molecular properties have been obtained from finite-field self-consistent field, Møller-Plesset perturbation theory and coupled cluster calculations with large, carefully optimized basis sets of gaussian-type functions. The mean dipole (hyper)polarizability and the mean quadrupole polarizability near the Hartree-Fock limit are alpha/e(2)a(0) (2)E(h) (-1) = 23.74 (HCCF), 37.26 (HCCCl), 43.97 (HCCBr), 56.44 (HCCI), beta/e(3)a(0) (3)E(h) (-2) = -73.9 (HCCF), -67.0 (HCCCl), -39.5 (HCCBr), 42.7 (HCCI), gamma/e(4)a(0) (4)E(h) (-3) = 4,914 (HCCF), 6,554 (HCCCl), 9,328 (HCCBr), 14,949 (HCCI), and C/e(2)a(0) (4)E(h) (-1) = 160.3 (HCCF), 317.1 (HCCCl), 471.2 (HCCBr), 671.2 (HCCI). Electron correlation has a small effect on the dipole polarizability but affects strongly the hyperpolarizability. Agreement with the available experimental data is more or less fair for HCCF, HCCCl, and HCCBr but less satisfactory for HCCI.

show abstract

Section: Introductionmentioning

confidence: 99%

Ab initio determination of the electric multipole moments and static (hyper)polarizability of HCCX, X = F, Cl, Br, and I

Maroulis

2003

J Comput Chem

View full text Add to dashboard Cite

show abstract

“…At high densities, the molecules can modify each others' structure and the apparent polarizability of colliding molecules can be different from that of the isolated molecules. The difference, the incremental polarizability can be studied by collision-induced light scattering 43,44 . The effect of anisotropic, tensorial polarizability can also be important at high densities 45 .…”

Section: Discussionmentioning

confidence: 99%

Correction to the Clausius–Mosotti equation: The dielectric constant of nonpolar fluids from Monte Carlo simulations

Valiskó

Boda

2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

We examine the dielectric constant of non-polar fluids by direct Monte Carlo simulations on the basis of the polarizable hard sphere (PHS) model where the spheres carry molecular polarizabilities.Point dipoles are induced in the spheres partly by an external electric field and partly by other molecules. It has been known that the Clausius-Mosotti equation needs a correction due to mutual polarization between molecules. We reproduce the qualitative behavior found in experiments: the correction increases with increasing density, reaches a maximum, and decreases at high densities.We show that the classic theory of Kirkwood and Yvon is quantitatively correct for the PHS model.

show abstract

“…8 At least two studies, employing high-resolution spectroscopy, have been devoted a) Electronic mail: michel.chrysos@univ-angers.fr to the infrared spectrum of that IR-active fundamental. 9,10 In a different context entirely, collision-induced Raman or hyper-Rayleigh processes involving sulfur hexafluoride have aroused keen interest in scientists in the last two decades, [11][12][13][14][15][16] reviving interest both in collision-induced processes [17][18][19][20] and in vibrational molecular spectroscopy. [21][22][23] More recently, SF 6 became the molecule of choice for testing a new spectroscopic probe, which uses impulsive stimulated Raman scattering and coherent electrons from high harmonic generation to monitor molecular dynamics.…”

Section: Introductionmentioning

confidence: 99%

The 2ν3 Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

Chrysos

Rachet

Kremer

2014

The Journal of Chemical Physics

View full text Add to dashboard Cite

Of the six normal vibrations of SF6, ν3 has a key role in the mechanisms of radiative forcing. This vibration, though inactive in Raman, shows up through the transition 2ν3 allowing for a complementary view on the asymmetric stretch of the molecule. Here, we look back into this topic, which has already caught some interest in the past but with some points been left out. We make a systematic incoherent-light-scattering analysis of the overtone with the use of different gas pressures and polarization orientations for the incident beam. Absolute-scale isotropic and anisotropic spectra are reported along with natural and pressure-induced widths and shifts, and other spectral features such as the peaks corresponding to the (experimentally indistinguishable) interfering channels Eg and F2g hitherto seen solely as two-photon IR-absorption features. We make the first-ever prediction of the SF6 polarizability second derivative with respect to the ν3-mode coordinate and we develop a heuristic argument to explain why the superposition of the three degenerate stretching motions that are related to the ν3 mode cannot but generate a polarized Raman band.

show abstract

Multipolar Polarizabilities from Interaction-induced Raman Scattering

Abstract: ISBN 9780471389309 Mots-clés collision-induced scattering (CIS) [4], isotropic molecules [5], Light scattering [6], Raman vibrational bands [7], Rayleigh frequencey region [8]

Cited by 22 publications

References 0 publications

Ab initio determination of the electric multipole moments and static (hyper)polarizability of HCCX, X = F, Cl, Br, and I

Ab initio determination of the electric multipole moments and static (hyper)polarizability of HCCX, X = F, Cl, Br, and I

Correction to the Clausius–Mosotti equation: The dielectric constant of nonpolar fluids from Monte Carlo simulations

The 2ν3 Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

Contact Info

Product

Resources

About