Similarities in the Intensities of Analogous Rydberg–Rydberg Transitions in the Molecular Series CF x Cl y (x=3, 2, 1; y=1, 2, 3)

Martı́n, I.; Mayor, E.; Velasco, A. M.

doi:10.1007/s00214-006-0107-3

Cited by 5 publications

(7 citation statements)

References 20 publications

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“…The doubly augmented orbitals (which are used to describe the Rydberg orbitals) have been centered on the Cl atom, based on previous results obtained for the CF 3 Cl molecule. 19,27,33 Similarly to what has been obtained for the CF 3 Cl molecule, preliminary results indicated that the location of the basis set used to describe the Rydberg orbitals is of secondary importance.…”

Section: A Computational Detailssupporting

confidence: 57%

“…The symmetry plane corresponds to the yz plane, and the z axis is in the direction of the C-Cl bond. The actual symmetry of the molecule (C s ) has been used in all 27,28 as it will be discussed later. The first step in the performed calculations consisted of a complete active state-averaged (CASSCF) calculation 29 where the same weight was given to all states considered.…”

Section: A Computational Detailsmentioning

confidence: 99%

“…The atomic orbitals (AO) integrals and AO gradient integrals were computed with program modules taken from DALTON. 40 In order to further test the accuracy of our highest level results (at the MR-CISD+Q level) the vertical excitation energies obtained at this level have been used to calculate the quantum defects for the 4s and 4p Rydberg states, through fitting to the Rydberg equation: 27…”

Section: A Computational Detailsmentioning

confidence: 99%

“…The calculated ionization energy of the HCFC-133a molecule at the CBS level is 12.25 eV, i.e., about 0.7 eV lower than the ionization energy of the Cl atom. 27,57 The average quantum defects for the n-4s and n-4p Rydberg states, obtained through fitting of the vertical excitation energies calculated at the MR-CISD+Q level to the Rydberg formula (see Sec. II A) are 2.13 and 1.79, respectively, in good agreement with the corresponding values of 2.09 and 1.68 reported for the Cl atom.…”

Section: Excited States Calculationsmentioning

confidence: 99%

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Matrix isolation infrared spectroscopic and theoretical study of 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

Rodrigues

Júnior

Ventura

et al. 2013

The Journal of Chemical Physics

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The molecular structure and infrared spectrum of the atmospheric pollutant 1,1,1-trifluoro-2-chloroethane (HCFC-133a; CF3CH2Cl) in the ground electronic state were characterized experimentally and theoretically. Excited state calculations (at the CASSCF, MR-CISD, and MR-CISD+Q levels) have also been performed in the range up to ~9.8 eV. The theoretical calculations show the existence of one (staggered) conformer, which has been identified spectroscopically for the monomeric compound isolated in cryogenic (~10 K) argon and xenon matrices. The observed infrared spectra of the matrix-isolated HCFC-133a were interpreted with the aid of MP2/aug-cc-pVTZ calculations and normal coordinate analysis, which allowed a detailed assignment of the observed spectra to be carried out, including identification of bands due to different isotopologues ((35)Cl and (37)Cl containing molecules). The calculated energies of the several excited states along with the values of oscillator strengths and previous results obtained for CFCs and HCFCs suggest that the previously reported photolyses of the title compound at 147 and 123.6 nm [T. Ichimura, A. W. Kirk, and E. Tschuikow-Roux, J. Phys. Chem. 81, 1153 (1977)] are likely to be initiated in the n-4s and n-4p Rydberg states, respectively.

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Section: A Computational Detailssupporting

confidence: 57%

Section: A Computational Detailsmentioning

confidence: 99%

Section: A Computational Detailsmentioning

confidence: 99%

Section: Excited States Calculationsmentioning

confidence: 99%

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Matrix isolation infrared spectroscopic and theoretical study of 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

Rodrigues

Júnior

Ventura

et al. 2013

The Journal of Chemical Physics

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“…For the HCFC-133a molecule, a considerable admixture of Cl (Rydberg) and C (valence) orbitals is obtained, thus masking the assignment of the Rydberg orbitals. However, accurate calculations of the energies of the 4s and 4p Rydberg states and the ionization potential (IP) of the Cl lone pair yield quantum defects that are consistent with the values obtained for the s and p series of the chlorine atom [24][25][26].…”

mentioning

confidence: 91%

Accurate calculation of the ionization energies of the chlorine lone pairs in 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

et al. 2014

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The vertical ionization energies of the chlorine lone pairs in HCFC-133a have been calculated at the SCF (via Koopmans' theorem and including orbital relaxation) and correlated (ROMP2, OVGF, and ROCCSD(T)) levels. Dunning aug-cc-pVXZ (X = D, T, and Q) basis sets were employed, and the ROMP2 and ROCCSD(T) results were extrapolated to the complete basis set (CBS) limit. Our highest-level results (obtained at the ROCCSD(T)/CBS level) were 11.99 and 12.08 eV for the Cl lone pairs of A″ and A' symmetry, respectively. The values obtained at the computationally much less demanding ROMP2/CBS level were just 0.10 and 0.13 eV higher than the highest-level ones. Using the Cl lone-pair band of the photoelectron spectrum of the HCF(2)Cl and CF(3)Cl molecules as a guide, it is considered very unlikely that these two lone pairs can be discriminated in the photoelectron spectrum of the title molecule. The use of the calculated IPs to estimate the energies of the Rydberg states of HCFC-133a is also discussed.

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Similarities in the continuous states of the group of halogenated methanes CH3X (X = Cl, Br, I): Molecular quantum defect orbital (MQDO) cross section calculations for allowed photoionization channels

Mayor

Velasco

Martı́n

2007

Chemical Physics Letters

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Similarities in the Intensities of Analogous Rydberg–Rydberg Transitions in the Molecular Series CF x Cl y (x=3, 2, 1; y=1, 2, 3)

Cited by 5 publications

References 20 publications

Matrix isolation infrared spectroscopic and theoretical study of 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

Matrix isolation infrared spectroscopic and theoretical study of 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

Accurate calculation of the ionization energies of the chlorine lone pairs in 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

Similarities in the continuous states of the group of halogenated methanes CH3X (X = Cl, Br, I): Molecular quantum defect orbital (MQDO) cross section calculations for allowed photoionization channels

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