44 research outputs found
More light on the 2ν5 Raman overtone of SF6: Can a weak anisotropic spectrum be due to a strong transition anisotropy?
No full textLong known as a fully polarized band with a near vanishing depolarization ratio [η s = 0.05, W. Holzer and R. Ouillon, Chem. Phys. Lett.24, 589 (1974)], the 2ν5 Raman overtone of SF6 has so far been considered as of having a prohibitively weak anisotropic spectrum [D. P. Shelton and L. Ulivi, J. Chem. Phys.89, 149 (1988)]. Here, we report the first anisotropic spectrum of this overtone, at room temperature and for 13 gas densities ranging between 2 and 27 amagat. This spectrum is 10 times broader and 50 times weaker than the isotropic counterpart of the overtone [D. Kremer, F. Rachet, and M. Chrysos, J. Chem. Phys.138, 174308 (2013)] and its profile much more sensitive to pressure effects than the profile of the isotropic spectrum. From our measurements an accurate value for the anisotropy matrix-element |⟨000020|Δα|000000⟩| was derived and this value was found to be comparable to that of the mean-polarizability ((000020),α¯¯,(000000)) . Among other conclusions our study offers compelling evidence that, in Raman spectroscopy, highly polarized bands or tiny depolarization ratios are not necessarily incompatible with large polarizability anisotropy transition matrix-elements. Our findings and the way to analyze them suggest that new strategies should be developed on the basis of the complementarity inherent in independent incoherent Raman experiments that run with two different incident-beam polarizations, and on concerted efforts to ab initiocalculate accurate data for first and second polarizability derivatives. Values for these derivatives are still rarities in the literature of SF6
The depolarized Raman 2 nu(3) overtone of CO2: A line-mixing shape analysis
No full textIn a recent article we showed that the 2 nu(3) transition of CO2 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 CO2 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
The isotropic remnant of the CO2 near-fully depolarized Raman 2v3 overtone
No full textIn a recent paper [M. Chrysos, I. A. Verzhbitskiy, F. Rachet, and A. P. Kouzov, J. Chem. Phys. 134, 044318 (2011)], we showed that, in CO2, the 2 nu(3) transition generates a Raman line spectrum that is 98% depolarized, a property in agreement with general symmetry rules. Here, we present an extensive analysis, experimental and theoretical, of the isotropic remnant of this overtone. The isotropic spectrum turned out to be 45 times less intense than its anisotropic counterpart and to have a moment that is 350 times smaller than the moment of the anisotropic spectrum, in excellent agreement with theoretical predictions. Once the measured intensity (along with other data exclusively experimental) was fed back into the formula of the moment, a value for the CO2 mean-polarizability asymmetric stretch derivative partial derivative(2)(alpha) over bar/partial derivative q(3)(2) was returned that matches the best ab initio prediction to better than 4%. Agreement, in order of magnitude, was found between the intensity reported herein and that reported in the sole prior study of this overtone [G. Tejeda, B. Mate, and S. Montero, J. Chem. Phys. 103, 568 (1995)]. (C) 2011 American Institute of Physics. [doi:10.1063/1.3557820
Heavy rare-gas atomic pairs and the “double penalty” issue: Isotropic Raman lineshapes by Kr2, Xe2, and KrXe at room temperature
No full textWe report absolutely calibrated isotropic Raman lineshapes for Kr2 and Xe2 and for KrXe at 294.5 K and compare them to quantum-mechanically generated lineshapes by using state-of-the-art second-order Møller-Plesset and DFT/B3LYP data sets for the induced mean dipole polarizability ᾱ . A very good agreement between the numerical and the experimental data was observed but the large uncertainty margins and the short Raman frequency interval probed in our experiment prevented us from rating on a more refined scale the performance of the tested ᾱ models. These drawbacks are inherent in isotropic Raman spectrum measurements and amplified for dissimilar pairs because, for such systems and spectra, the unreliable operation of subtracting optical signals of comparable magnitude occurs twice per Raman frequency shift value, thus penalizing twice the quality of the measured data. In light of our findings and of previously reported evidence about related electric properties in Kr2 and Xe2 and in KrXe, we are left with no doubt as to the consistency of the induced-polarizability and interatomic-potential data used for these three systems at the reported level of accuracy
Collision-induced Raman scattering and the peculiar case of neon: Anisotropic spectrum, anisotropy, and the inverse scattering problem
No full textOwing in part to the p orbitals of its filled L shell, neon has repeatedly come on stage for its peculiar properties. In the context of collision-induced Raman spectroscopy, in particular, we have shown, in a brief report published a few years ago [M. Chrysos et al., Phys. Rev. A 80, 054701 (2009)], that the room-temperature anisotropic Raman lineshape of Ne–Ne exhibits, in the far wing of the spectrum, a peculiar structure with an aspect other than a smooth wing (on a logarithmic plot) which contrasts with any of the existing studies, and whose explanation lies in the distinct way in which overlap and exchange interactions interfere with the classical electrostatic ones in making the polarizability anisotropy, α ∥ − α ⊥. Here, we delve deeper into that study by reporting data for that spectrum up to 450 cm−1 and for even- and odd-order spectral moments up to M 6, as well as quantum lineshapes, generated from SCF, CCSD, and CCSD(T) models for α ∥ − α ⊥, which are critically compared with the experiment. On account of the knowledge of the spectrum over the augmented frequency domain, we show how the inverse scattering problem can be tackled both effectively and economically, and we report an analytic function for the anisotropy whose quantum lineshape faithfully reproduces our observations
Collision-induced Raman scattering by rare-gas atoms: The isotropic spectrum of Ne–Ne and its mean polarizability
No full textWe report the room-temperature isotropic collision-induced light scattering spectrum of Ne–Ne over a wide interval of Raman shifts, and we compare it with the only available experimentalspectrum for that system as well as with spectra calculated quantum-mechanically with the employ of advanced ab initio -computed data for the incremental mean polarizability. Thespectral range previously limited to 170 cm−1 is now extended to 485 cm−1 allowing us to successfully solve the inverse-scattering problem toward an analytic model for the meanpolarizability that perfectly matches our measurements. We also report the depolarization ratio of the scattering process, lingering over the usefulness of this property for more stringent checks between the various polarizability models
On the isotropic Raman spectrum of Ar2 and how to benchmark ab initio calculations of small atomic clusters: Paradox lost
No full textThis is the long-overdue answer to the discrepancies observed between theory and experiment in Ar2 regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, BR [Gaye et al., Phys. Rev. A 55, 3484 (1997)]. At the origin of this progress is the advent (posterior to 1997) of advanced computational methods for weakly interconnected neutral species at close separations. Here, we report agreement between the previously taken Raman measurements and quantum lineshapes now computed with the employ of large-scale CCSD or smartly constructed MP2 induced-polarizability data. By using these measurements as a benchmark tool, we assess the degree of performance of various other ab initio computed data for the mean polarizability α, and we show that an excellent agreement with the most recently measured value of BR is reached. We propose an even more refined model for α, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed
Isotropic and anisotropic collision-induced Raman scattering by monoatomic gas mixtures: Ne-Ar
No full textWe report the long-overdue collision-induced Raman scattering spectrum by a pair of unlike rare gas atoms. Absolute-unit scattering intensities, both isotropic and anisotropic, are given for Ne-Ar, along with the depolarization ratio for this system, recorded by a gaseous room-temperature mixture over a wide range of frequency shift. We make a critical comparison with spectra computed quantum-mechanically on the basis of modern pair-polarizability representations for Ne-Ar, of either ab initio or density functional theory methods. We report a value for the Kerr second virial coefficient, deduced from our measurements. Our data are especially intended to add to the vital yet hitherto incomplete knowledge of the role of collision-induced processes in atmospheric environments
Estimating excess hazard ratios and net survival when covariate data are missing: strategies for multiple imputation.
No full textBACKGROUND: Net survival is the survival probability we would observe if the disease under study were the only cause of death. When estimated from routinely collected population-based cancer registry data, this indicator is a key metric for cancer control. Unfortunately, such data typically contain a non-negligible proportion of missing values on important prognostic factors (eg, tumor stage). METHODS: We carried out an empirical study to compare the performance of complete records analysis and several multiple imputation strategies when net survival is estimated via a flexible parametric proportional hazards model that includes stage, a partially observed categorical covariate. Starting from fully observed cancer registry data, we induced missingness on stage under three scenarios. For each of these scenarios, we simulated 100 incomplete datasets and evaluated the performance of the different strategies. RESULTS: Ordinal logistic models are not suitable for the imputation of tumor stage. Complete records analysis may lead to grossly misleading estimates of net survival, even when the missing data mechanism is conditionally independent of survival time given the covariates and the bias on the excess hazard ratios estimates is negligible. CONCLUSIONS: As key covariates are unlikely missing completely at random, studies estimating net survival should not use complete records. When the missingness can be inferred from available data, appropriate multiple imputation should be performed. In the context of flexible parametric proportional hazards models with a partially observed stage covariate, a multinomial logistic imputation model for stage should be used and should include the Nelson-Aalen cumulative hazard estimate and the event indicator
Controllable transport of water through nanochannel by rachet-like mechanism
No full textAuthor name used in this publication: Yang Liu2011-2012 > Academic research: refereed > Publication in refereed journalVersion of RecordPublishedVoR allowe
