The vibrational frequencies of CaO 2 , ScO 2 , and TiO 2 : a comparison of theoretical methods

Rosi, Marzio; Bauschlicher, Charles W.; Chertihin, George V.; Andrews, Lester

doi:10.1007/s002140050311

Cited by 35 publications

(48 citation statements)

References 23 publications

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“…While experience has shown that the DFT approaches can treat a very large number of systems accurately, even these approaches are susceptible to symmetry-breaking, as we have discussed previously [11] for metal-containing systems and show for an organic system in this report. Our experience has been that the geometries and frequencies are very similar at the B3LYP and BP86 levels of theory, but, in general, the B3LYP approach works somewhat better for organic molecules, while, in general, the BP86 works better for organometallic compounds.…”

Section: Introductionmentioning

confidence: 61%

The infrared spectra of polycyclic aromatic hydrocarbons containing a five-membered ring: symmetry breaking and the B3LYP functional

Bauschlicher

Hudgins

Allamandola

1999

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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The infrared spectra of six molecules, each of which contains a ®ve-membered ring, and their cations are determined using density functional theory; both the B3LYP and BP86 functionals are used. The computed results are compared with the experimental spectra. For the neutral molecules, both methods are in good agreement with experiment. Even the Hartree±Fock (HF) approach is qualitatively correct for the neutral species. For the cations, the HF approach fails, as found for other organic ring systems. The B3LYP and BP86 approaches are in good mutual agreement for ®ve of the six cation spectra, and are in good agreement with experiment for four of the ®ve cations where the experimental spectra are available. It is only for thē uoranthene cation where the BP86 and B3LYP functionals yield dierent results; the BP86 approach yields the expected g 2v symmetry, while the B3LYP approach breaks symmetry. The experimental spectra support the BP86 spectra over the B3LYP spectra, but the quality of the experimental spectra does not allow a critical evaluation of the accuracy of the BP86 approach for this dicult system.

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Section: Introductionmentioning

confidence: 61%

The infrared spectra of polycyclic aromatic hydrocarbons containing a five-membered ring: symmetry breaking and the B3LYP functional

Bauschlicher

Hudgins

Allamandola

1999

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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“…A similar approach is applied here to the CrO n Ϫ series, especially for nϭ3 -5, for which there is little previous work. Among the 3d TM oxide anions, theoretical studies have been performed for ScO 2 Ϫ , [20][21][22] TiO n Ϫ , 23 VO n Ϫ , 24 MnO n Ϫ , 14,25,26 and FeO n Ϫ , 27,28 and good agreement between experimental data and the calculated EA's of the corresponding neutral species has generally been obtained. Detailed studies of the electronic and geometrical structure of the neutral and anionic 3d TM monoxides 29 and dioxides 30 have been performed using DFT methods with different generalized gradient approximations for the exchange-correlation functional.…”

Section: Introductionmentioning

confidence: 77%

Electronic structure of chromium oxides, CrOn− and CrOn (n=1–5) from photoelectron spectroscopy and density functional theory calculations

Gutsev

Jena

Zhai

et al. 2001

The Journal of Chemical Physics

123

119

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The electronic structure of CrO n Ϫ and CrO n (nϭ1-5) was investigated using anion photoelectron spectroscopy and density functional theory. Photoelectron spectra of CrO n Ϫ were obtained at several photon energies and yielded electron affinities, vibrational and electronic structure information about the neutral CrO n species. Density functional theory calculations were carried out for both the neutrals and anions and were used to interpret the experimental spectra. Several low-lying electronic states of CrO were observed and assigned from photodetachment of the CrO Ϫ ground state (6 ͚ ϩ) and an excited state (4 ͟), which is only 0.1 eV higher. The main spectral features of CrO 2 Ϫ were interpreted based on a C 2v CrO 2 Ϫ (4 B 1). A very weak Cr͑O 2) Ϫ isomer was also observed with lower electron binding energies. Relatively simple and vibrationally resolved spectra were observed for CrO 3 Ϫ , which was determined to be D 3h. The CrO 3 neutral was calculated to be C 3v with the Cr atom slightly out of the plane of the three O atoms. The spectrum of CrO 4 Ϫ revealed a very high electron binding energy. Several isomers of CrO 4 Ϫ were predicted and the ground state has a distorted tetrahedral structure (C 2) without any O-O bonding. Only one stable structure was predicted for CrO 5 Ϫ with a superoxo O 2 bonded to a C 3v CrO 3 .

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“…Geometric predictions made by the B3LYP and BP86 methods are similar, although it seems that the BP86 functional produces more accurate vibrational frequencies, in agreement with earlier theoretical work by Rosi and others. 39 The predicted adiabatic and vertical electron affinity and dissociation energy of TiO 2 and the vertical detachment energy of TiO 2 Ϫ are listed in Table IV. All levels of theory are in excellent agreement ͑within 0.1 eV͒ with the experimental value for the electron affinity of TiO 2 .…”

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confidence: 99%

The structures, electron affinities, and energetic stabilities of TiOn and TiOn− (n=1–3)

Walsh¹,

King²,

Schaefer³

1999

The Journal of Chemical Physics

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By use of density functional and coupled cluster methods, we report energetic and structural information concerning the ground states of TiOn and TiOn− (n=1–3), much of which has not previously been observed experimentally or predicted theoretically. This study establishes the following geometrical symmetries and electronic ground states: X̃ 1A′ TiO3 (Cs), X̃ 2A2′ or B22 TiO3− (D3h or C2v), and X̃ 2A1 TiO2− (C2v). In addition, the electronic ground state of TiO− is established as Δ,2 arising from the 9σ21δ configuration. This finding is contrary to the suggestion of Wu and Wang, contained in their report of recent photoelectron experiments, that ground state TiO− has a 9σ1δ2 electronic configuration and Σ−4 symmetry. The ground state minimum-energy structure for TiO3− contains no oxygen–oxygen bonds and has D3h or C2v symmetry. The first theoretical adiabatic electron affinities, as predicted by the CCSD(T)//B3LYP level of theory, for TiO, TiO2, and TiO3 are 1.25 eV, 1.60 eV, and 3.34 eV, while Wu and Wang’s photoelectron measurements for these were 1.30 eV, 1.59 eV, and 4.2 eV, respectively. The results for the mon- and dioxide cases are in excellent accord with experiment; however, the experimental result for TiO3 is approached with similar accuracy only when compared with our CCSD(T)//B3LYP value for the vertical detachment energy for TiO3− of 4.02 eV. The latter prediction reflects the fact that the theoretical structures for TiO3 and TiO3− are qualitatively different. Finally, several of the lowest-lying minima on the potential energy surfaces of TiO3 and TiO3− are elucidated.

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The vibrational frequencies of CaO 2 , ScO 2 , and TiO 2 : a comparison of theoretical methods

Cited by 35 publications

References 23 publications

The infrared spectra of polycyclic aromatic hydrocarbons containing a five-membered ring: symmetry breaking and the B3LYP functional

The infrared spectra of polycyclic aromatic hydrocarbons containing a five-membered ring: symmetry breaking and the B3LYP functional

Electronic structure of chromium oxides, CrOn− and CrOn (n=1–5) from photoelectron spectroscopy and density functional theory calculations

The structures, electron affinities, and energetic stabilities of TiOn and TiOn− (n=1–3)

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