CCSD(T) calculations of vibrational frequencies and equilibrium geometries for the diatomics F2, SF, and their ions

Živný, Oldřich; Czernek, Jiřı́

doi:10.1016/s0009-2614(99)00603-x

Cited by 20 publications

(12 citation statements)

References 17 publications

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“…These calculations offer an improvement over other, mostly earlier results. [60][61][62][63][64][65][66][67][68] Additional spectroscopic constants have been calculated by ab initio means by various authors [69][70][71][72][73][74][75] employing relatively large basis sets and reasonably high levels of theory, with and without core correlations, but without relativistic corrections. Earlier work is based on relatively small basis sets.…”

Section: Introductionmentioning

confidence: 99%

Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

Bytautas

Matsunaga

Nagata

et al. 2007

The Journal of Chemical Physics

134

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An analytical expression is found for the accurate ab initiopotential energy curve of the fluorine molecule that has been determined in the preceding two papers. With it, the vibrational and rotational energy levels of F2 are calculated using the discrete variable representation. The comparison of this theoretical spectrum with the experimental spectrum, which had been measured earlier using high-resolution electronic spectroscopy, yields a mean absolute deviation of about 5cm−1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30cm−1 of the experimental value of 12953±8cm−1. The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation,spin-orbit coupling, and scalar relativity. The Dunham analysis [Phys. Rev.41, 721 (1932)] of the spectrum is found to be very accurate. New values are given for the spectroscopic constants. KeywordsAb initio calculations, Dissociation energies, Polynomials, Dissociation, Electron correlation calculations Disciplines Chemistry CommentsThe following article appeared in Journal of Chemical Physics 127 (2007) An analytical expression is found for the accurate ab initio potential energy curve of the fluorine molecule that has been determined in the preceding two papers. With it, the vibrational and rotational energy levels of F 2 are calculated using the discrete variable representation. The comparison of this theoretical spectrum with the experimental spectrum, which had been measured earlier using high-resolution electronic spectroscopy, yields a mean absolute deviation of about 5 cm −1 over the 22 levels. The dissociation energy with respect to the lowest vibrational energy is calculated within 30 cm −1 of the experimental value of 12 953± 8 cm −1 . The reported agreement of the theoretical spectrum and dissociation energy with experiment is contingent upon the inclusion of the effects of core-generated electron correlation, spin-orbit coupling, and scalar relativity. The Dunham analysis ͓Phys. Rev. 41, 721 ͑1932͔͒ of the spectrum is found to be very accurate. New values are given for the spectroscopic constants.

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Section: Introductionmentioning

confidence: 99%

Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

Bytautas

Matsunaga

Nagata

et al. 2007

The Journal of Chemical Physics

134

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“…They calculated the properties of the ground state using Hartree-Fock ͑HF͒ wave functions. [23][24][25][26][27][28][29] The excited electronic states are of great importance in interpreting the optical properties of molecules. Staemmler 22 studied the vibrational frequencies of the SF radical using the coupled electron pair approximation ͑CEPA͒ in 1982.…”

Section: Introductionmentioning

confidence: 99%

Ground and valence-excited states of SF: A multireference configuration interaction with single and double excitations+Q study

Yang

Boggs

2005

The Journal of Chemical Physics

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Ab initio calculations on the ground and valence-excited states of the sulfur monofluoride radical have been performed using entirely uncontracted all-electron augmented correlation consistent polarized valence quintuple zeta basis sets and the internally contracted multireference configuration interaction with single and double excitations method and Davidson correction (+Q). Potential-energy curves of all valence electronic states and the spectroscopic constants of several bound states are fitted. It is the first time that the entire 27-omega states generated from the 12 valence lambda-S states which come from the S(3P(g)) and F(2P(u)) atomic states of SF radical have been studied theoretically. The effects of spin-orbit coupling and the avoided crossing rule between omega states of the same symmetry are analyzed. The calculated results reproduce well the available experimental values and predict the properties of several bound excited states that have never been observed in experiment. The transition properties of the dipole-allowed transitions from bound excited states to the ground state are predicted for the first time, including the transition dipole moments, the Franck-Condon factors, and the radiative lifetimes.

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“…A number of high-quality computational 13,14,[18][19][20][21] and experimental [22][23][24][25] studies have been undertaken on F 2 and its molecular cation F + 2 (see also references contained in citations). Because of its pathological electronic structure, in which the mean-field (Hartree-Fock, HF) solution is spin-polarized already at the equilibrium geometry, F 2 has provided an excellent test case for ab initio method development.…”

Section: Neutral and Cation Ground Statesmentioning

confidence: 99%

Simulation of X-ray transient absorption for following vibrations in coherently ionized F2 molecules

Dutoi

Leone

2017

Chemical Physics

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Femtosecond and attosecond x-ray transient absorption experiments are becoming increasingly sophisticated tools for probing nuclear dynamics. In this work, we explore and develop theoretical tools needed for interpretation of such spectra, in order to characterize the vibrational coherences that result from ionizing a molecule in a strong IR field. Ab initio data for F 2 is combined with simulations of nuclear dynamics, in order to simulate time-resolved x-ray absorption spectra for vibrational wavepackets after coherent ionization at 0 K and at finite temperature. Dihalogens pose rather difficult electronic structure problems, and the issues encountered in this work will be reflective of those encountered with any core-valence excitation simulation when a bond is breaking. The simulations reveal a strong dependence of the x-ray absorption maximum on the locations of the vibrational wave packets. A Fourier transform of the simulated signal shows features at the overtone frequencies of both the neutral and the cation, which reflect spatial interferences of the vibrational eigenstates. This provides a direct path for implementing ultrafast x-ray spectroscopic methods to visualize coherent nuclear dynamics.

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CCSD(T) calculations of vibrational frequencies and equilibrium geometries for the diatomics F2, SF, and their ions

Cited by 20 publications

References 17 publications

Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

Accurate ab initio potential energy curve of F2. III. The vibration rotation spectrum

Ground and valence-excited states of SF: A multireference configuration interaction with single and double excitations+Q study

Simulation of X-ray transient absorption for following vibrations in coherently ionized F2 molecules

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