Pseudo-conformer models for linear molecules: Joint treatment of spectroscopic, electron diffraction and ab initio data for the C 3 O 2 molecule

Tarasov, Yury I.; Кочиков, И. В.

doi:10.1016/j.molstruc.2018.02.095

Cited by 2 publications

(3 citation statements)

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“…This barrier is negligible compared to the zero-point E of 0.13 kJ/mol for the C–C–C bending mode, whose calculated harmonic frequency is 22 cm –1 by M06-2X. This implies a large-amplitude bend and supports a recent study of C 3 O 2 , with MP2/cc-pVTZ showing the linear geometry to be at the minimum E but with MP2/6-311+G(d) giving a 9° deviation from linearity at the minimum E and a barrier to linearity of 0.05 kJ/mol …”

Section: Computational Methodssupporting

confidence: 80%

“…This implies a large-amplitude bend and supports a recent study of C 3 O 2 , with MP2/cc-pVTZ showing the linear geometry to be at the minimum E but with MP2/6-311+G(d) giving a 9°deviation from linearity at the minimum E and a barrier to linearity of 0.05 kJ/mol. 19 Adiabatic ionization energies are differences between the respective optimized E of the radical cation and the neutral molecule. For I, as for the R, B3LYP results with either basis set are close to the available experimental results, somewhat closer overall than M06-2X, and significantly closer than MP2.…”

Section: Methodsmentioning

confidence: 99%

“…Of the three computational methods, only M06-2X gives linear C 3 O 2 at a saddle point between stable C 2 v structures. See the text below. c Electron diffraction; ref . d A (CCC) deviations from linearity are 51° by UMP2, 32° by UM06-2X, and 22° by UB3LYP. e Ref . …”

Section: Computational Methodsmentioning

confidence: 99%

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Modeling the Chemistry of Gaseous Cations Derived from Tricarbon Dioxide

Schildcrout

2021

J. Phys. Chem. A

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Cations C p O q + (p ≤ 7 with q = 1,2) and C p O3 + (p = 4–7) and corresponding neutrals are modeled by B3LYP/jun-cc-pVTZ to rationalize previous mass spectrometric observations of ion reactions with neutral C3O2. Modeling yields optimized potential energies, geometries, Mulliken spin populations, electric dipole moments, electron configurations, and thermochemical parameters. Lewis diagrams are derived. Mono- and dioxide cations typically have unbranched carbon chains, but trioxides are branched. The ions are most stable as spin doublets, but low-lying quartets are found for monoxides with even p. For trioxide ions, the quartets for p = 5,7 are lower-lying than for p = 4,6. For neutral mono- and dioxides resulting from possible electron transfer to the ions, triplets are more stable than singlets for even p. Neutral trioxides are most stable as triplets except C5O3 with a singlet slightly more stable. Singlet C4O3 and C6O3 are unstable with respect to CO loss. Charge transfer is likely only for C p O+ (p = 1–3) and C p O3 + (p = 4, 6). Monocarbon insertion by C3O2 is understood as two sequential CO losses without a hypothetical C6O4 +• intermediate and is thermochemically favorable for all ions considered.

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Section: Computational Methodssupporting

confidence: 80%

Section: Methodsmentioning

confidence: 99%