The Raman spectra and cross-sections of the ν2 band of H2O, D2O, and HDO

Avila, Gustavo; Tejeda, Guzmán; Fernández, J. M.; Montero, S.

doi:10.1016/j.jms.2003.10.008

Cited by 14 publications

(22 citation statements)

References 22 publications

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“…These wavefunctions, jointly with a high-level ab initio, wavelength-dependent molecular polarizability surface, yield transition moments accurate enough to reproduce all the experimental data of the molecular polarizability of the water molecule available to date: (i) rotational Raman spectra of H 2 O, D 2 O, and HDO [1], (ii) rotational-vibrational Raman spectra of the m 2 band of H 2 O, D 2 O, and HDO [2], (iii) rotational-vibrational Raman spectra of the 2m 2 and m 1 /m 3 bands of H 2 O, D 2 O, and HDO, as reported here, (iv) absolute value of the mean polarizability (obtained from the molar refractivity [12]), and (v) depolarization ratio of the rotational Raman spectrum of H 2 O [13]. The wavefunctions and polarizability surface referred above can be used with reasonable confidence to simulate any region of the Raman spectrum of water vapor in the spectral range 0 < m < 5000 cm À1 up to $2000 K, the temperature of hydrocarbon/air combustion flames [14].…”

Section: Introductionmentioning

confidence: 93%

“…The conventions on axes orientation, vibrational coordinates, and symmetry notation employed here are the same as in our previous works [1,2,4]. The details about the variational calculation of the rovibrational wavefunctions from a Hamiltonian in Radau coordinates have been given in [2], and those of the ab initio (CCSD), wavelength-dependent, polarizability surface in [1,2].…”

Section: Theorymentioning

confidence: 99%

“…The details about the variational calculation of the rovibrational wavefunctions from a Hamiltonian in Radau coordinates have been given in [2], and those of the ab initio (CCSD), wavelength-dependent, polarizability surface in [1,2].…”

Section: Theorymentioning

confidence: 99%

“…In previous works we have reported the vapor phase Raman spectra of H 2 O, and of mixtures of D 2 O and HDO, at room temperature, in the regions of the rotational spectrum [1] and of the m 2 bending band [2]. These spectra were interpreted in terms of transition moments of a high-level ab initio molecular polarizability, employing variational rotational-vibrational wavefunctions considering the rotational-vibrational coupling in full.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The Raman spectra and cross-sections of H2O, D2O, and HDO in the OH/OD stretching regions

Avila

Fernández

Tejeda

et al. 2004

Journal of Molecular Spectroscopy

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Section: Introductionmentioning

confidence: 93%

Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The Raman spectra and cross-sections of H2O, D2O, and HDO in the OH/OD stretching regions

Avila

Fernández

Tejeda

et al. 2004

Journal of Molecular Spectroscopy

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“…[33][34][35] and references therein, which is, in turn, important for a number of ap plications including atmospheric studies using Lidar [36] and analysis of flames [37,38].…”

Section: Introductionmentioning

confidence: 99%

A database of water transitions from experiment and theory (IUPAC Technical Report)

Tennyson

Bernath

Brown

et al. 2014

Pure and Applied Chemistry

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Abstract:The report and results of an IUPAC Task Group (TG) formed in 2004 on "A Database of Water Transitions from Experiment and Theory" (Project No. 2004-035-1-100) O, are determined from measured transition frequencies. The transition frequencies and energy levels are validated using first-principles nuclear motion computations and the MARVEL (measured active rotational-vibrational energy levels) approach. The extensive data including lines and levels are required for analysis and synthesis of spectra, thermochemical applications, the construction of theoretical models, and the removal of spectral contamination by ubiquitous water lines. These datasets can also be used to assess where measurements are lacking for each isotopologue and to provide accurate frequencies for many yet-to-be measured transitions. The lack of high-quality frequency calibration standards in the near infrared is identified as an issue that has hindered the determination of high-accuracy energy levels at higher frequencies. The generation of spectra using the MARVEL energy levels combined with transition intensities computed using high accuracy ab initio dipole moment surfaces are discussed. A recommendation of the TG is for further work to identify a single, suitable model to represent pressure-(and temperature-) dependent line profiles more accurately than Voigt profiles.

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Calculation of absolute Raman scattering cross‐sections using vibrational self‐consistent field/vibrational configuration interaction wave functions

Carvalho

Vidal

2022

J Comput Chem

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In the present study, the differential scattering cross-sections, depolarization ratios and Raman shifts of small molecular systems are obtained from configuration iteration wave functions of vibrational self-consistent field (VSCF) states. The transition polarizabilities were modeled using the Placzek approximation, neglecting those contributions not arising from the electric dipole mechanism. This theoretical approach is considered a good approximation for samples that absorb in the UV range if the excitation radiation falls in the visible region, as is the case of the molecules selected for the present study, namely: water, methane, and acetylene. Potential energy and electronic polarizability surfaces are calculated by the CCSD(T) and CC3 methods with aug-cc-p(C)V(T,Q,5)Z basis sets. The vibrational Hamiltonian includes the vibrational angular momentum contribution of the Watson kinetic energy operator. As expected, due to the variational nature of the VSCF and vibrational configuration interaction (VCI) methods, the Raman transition wavenumbers are substantially improved over the harmonic predictions. Surprisingly, the scattering cross-sections obtained using the harmonic approximation or the VSCF method better agrees with the experimental values than those cross-sections predicted using VCI wave functions. The more significant deviations of the VCI results from the experimental reference may be related to the significant uncertainties of the measured cross-sections. Still, it may also indicate that the VCI Raman transition moments may require a more accurate description of the electronic polarizability surface. Finally, the depolarization ratios calculated for H 2 O and C 2 D 2 using harmonic and VCI wave functions have similar accuracy, whereas, for C 2 H 2 and C 2 HD, the VCI results are more accurate.

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The Raman spectra and cross-sections of the ν2 band of H2O, D2O, and HDO

Cited by 14 publications

References 22 publications

The Raman spectra and cross-sections of H2O, D2O, and HDO in the OH/OD stretching regions

The Raman spectra and cross-sections of H2O, D2O, and HDO in the OH/OD stretching regions

A database of water transitions from experiment and theory (IUPAC Technical Report)

Calculation of absolute Raman scattering cross‐sections using vibrational self‐consistent field/vibrational configuration interaction wave functions

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