Theoretical study of ScCO2+

Sodupe, Mariona; Branchadell, V.; Oliva, A.; Bertrán, Juan

doi:10.1002/(sici)1097-461x(1997)63:2<523::aid-qua21>3.0.co;2-7

Cited by 3 publications

(3 citation statements)

References 28 publications

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“…Thus, the B3LYP binding energies are superior to those obtained at the CCSD(T) level if the small basis set is used. For Sc + −CO 2 , the computed binding energy is about 6 kcal/mol larger than the MCPF value determined in our previous work, due to the differences in the basis set and to the fact that in the previous calculations the 3s and 3p electrons of Sc were not correlated.…”

Section: Resultscontrasting

confidence: 73%

“…12 For Sc + , the η 2 -C,O mode was found to be a minimum only at the Hartree-Fock level, while inclusion of electron correlation lead to the inserted OSc + CO structure. 15 On the basis of these test calculations, we have only considered the linear M + -OCO coordination and the inserted structure OM + CO in the remaining systems.…”

Section: Resultsmentioning

confidence: 99%

“…9 On the other hand, for V + CO 2 , the inserted OV + CO isomer has been shown to be more stable than the electrostatically bound V + -CO 2 structure. 5 As in the case of ScCO 2 + , 15 the larger stability of the inserted isomer is due to the fact that early transition metals form strong metal-oxide bonds, 16 and thus, a different behavior between early and late transition metals is expected. Other experimental works have studied the interaction of carbon dioxide with non-transition metal cations.…”

Section: Introductionmentioning

confidence: 98%

See 2 more Smart Citations

Theoretical Study of M⁺−CO₂ and OM⁺CO Systems for First Transition Row Metal Atoms

Sodupe¹,

Branchadell²,

Rosi³

et al. 1997

J. Phys. Chem. A

118

160

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The coordination of carbon dioxide to first transition row metal cations and the insertion reaction of the metal into one CO bond of carbon dioxide have been studied theoretically. The geometry and the vibrational frequencies of the M+−CO2 and OM+CO structures have been determined using the hybrid three-parameter B3LYP density functional approach. Binding energies have also been determined at the CCSD(T) level using large basis sets. The linear end-on M+−OCO structure is the most favorable coordination for CO2, due to the electrostatic nature of the bonding. In the inserted OM+CO structures, the bonding arises from the electrostatic interaction between the ground state of OM+ and CO. For the early transition metals (Sc+, Ti+, and V+), the insertion reaction is exothermic and the inserted OM+CO structure is more stable than the linear M+−OCO isomer, because of the very strong MO+ bond that is formed.

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Section: Resultscontrasting

confidence: 73%

Section: Resultsmentioning

confidence: 99%