Thermochemistry of the reactions of F+(3P) and F+(1D) with hydrogen sulphide: a molecular orbital study

Manuel, M.; Mó, Otília; Yáñez, Manuel

doi:10.1080/00268979709482740

Cited by 3 publications

(3 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Probably the most significant one is the energy gap between F + ( 1 D) and F + ( 3 P). The G3X calculated value (61.3 kcal mol -1 ) is in very good agreement with previous theoretical estimates obtained at the G2-level (62.1 kcal mol -1 ) 15,19 as well as with the experimental value (59.7 kcal mol -1 ). 65 However, the B3LYP/6-311+G(3df,2p) value (83.2 kcal mol -1 ) dramatically overestimates this energy difference.…”

Section: Resultssupporting

confidence: 91%

“…[4][5][6][7] In this respect the role of high-level ab initio molecular orbital techniques [8][9][10][11][12][13] was of great importance in elucidating these mechanisms. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Actually, in many occasions, the ab initio or density functional theory calculations are the only alternative available to investigate the structures of ionic species, which, very often, are elusive to experimental observation. Besides, high-level theoretical methods reach the so-called chemical accuracy, and therefore, many thermodynamic properties of neutral and charged species can be estimated within (2.0 kcal/mol of the experimental values, when available.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reactions of F⁺(³P) and F⁺(¹D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

et al. 2006

View full text Add to dashboard Cite

High level ab initio and density functional theory calculations have been carried out to study the potential energy surfaces associated with the reactions of F(+) in its (3)P ground state and in its (1)D first excited state with silicon dioxide. The structures and vibrational frequencies of the stationary points of both potential energy surfaces were obtained at the B3LYP/6-31G(d) level. Final energies were calculated at the B3LYP/6-311+G(3df,2p) and at the G3X levels of theory. [Si, O(2), F](+) singlet and triplet state cations present very different bonding characteristics. The most favorable reactions path in F(+)((3)P) + SiO(2) reactions should yield O(2) + SiF(+), while in the reactions in the first excited state, only a charge exchange process, yielding F((2)P) + SiO(2)(+)((2)A), should be observed. However, both potential energy surfaces cross each other, because although the entrance F(+)((3)P) + SiO(2) lies 34.5 kcal/mol below F(+)((1)D) + SiO(2), the global minimum of the singlet PES lies 10.3 kcal/mol below the global minimum of the triplet. The minimum energy crossing point between them is close to the global minimum, and the spin-orbit coupling is not zero, suggesting that very likely some of the products will be formed in the singlet hypersurface. The existence of instabilities and large spin-contamination in the description of some of the systems render the DFT calculations unreliable.

show abstract

Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Reactions of F⁺(³P) and F⁺(¹D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

et al. 2006

View full text Add to dashboard Cite

show abstract

“…This is the case of the halogen cations and N + where the first excited 1 D state is relatively close in energy to the ground 3 P state. 22 Quite importantly, however, when the ion is attached to a neutral molecule, a reverse stability order is often found and singlets become lower in energy than triplets, 8,13,[23][24][25][26][27][28] reflecting the stronger bonds between the ion and the neutral in the former. Accordingly, different crossovers between singlet and triplet PESs can be envisaged, 13,26,28 and therefore in many of these processes spin-forbidden reaction mechanisms play an important role, as has been suggested before for N + + SH 2 and N + + H 2 CO reactions.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Survey of the Potential Energy Surfaces Associated with the N⁺(³P,D) + C₂H₄Reactions in the Gas Phase

2004

View full text Add to dashboard Cite

The potential energy surfaces (PESs) associated with the reactions between ethylene and N+(3P,1D) ions have been investigated through the use of high-level G2(MP2) ab initio calculations. Although the N+(3P) + C2H4 entrance channel lies 46.7 kcal mol-1 below the N+(1D) + C2H4, most of the singlet-state cations are more stable than their triplet-state counterparts because, in general, the bonds in the former are stronger than those in the latter, favoring the crossover between both PESs. Several minimum energy crossing points between both hypersurfaces have been located, and the corresponding spin−orbit couplings indicate that spin-forbidden processes in N+ + C2H4 reactions cannot be discarded. According to our survey, the product distribution in both N+(3P) + C2H4 and N+(1D) + C2H4 reactions should be quite different. While for the triplets the CNH+, HCNH+, HCCH2 +, and HCCH+ product ions should be observed, in agreement with the available experimental information, for the singlets the formation of CH3 + should be the dominant process.

show abstract

The role of spin-forbidden processes in N+(3P) + NH3 reactions in the gas phase

Ijjaali¹,

El‐Mouhtadi²,

Esseffar³

et al. 2001

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Thermochemistry of the reactions of F+(3P) and F+(1D) with hydrogen sulphide: a molecular orbital study

Cited by 3 publications

References 22 publications

Reactions of F⁺(³P) and F⁺(¹D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

Reactions of F⁺(³P) and F⁺(¹D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

Theoretical Survey of the Potential Energy Surfaces Associated with the N⁺(³P,D) + C₂H₄Reactions in the Gas Phase

The role of spin-forbidden processes in N+(3P) + NH3 reactions in the gas phase

Contact Info

Product

Resources

About

Thermochemistry of the reactions of F+(3P) and F+(1D) with hydrogen sulphide: a molecular orbital study

Cited by 3 publications

References 22 publications

Reactions of F+(3P) and F+(1D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

Reactions of F+(3P) and F+(1D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

Theoretical Survey of the Potential Energy Surfaces Associated with the N+(3P,D) + C2H4Reactions in the Gas Phase

The role of spin-forbidden processes in N+(3P) + NH3 reactions in the gas phase

Contact Info

Product

Resources

About

Reactions of F⁺(³P) and F⁺(¹D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

Reactions of F⁺(³P) and F⁺(¹D) with Silicon Oxide. Possibility of Spin-Forbidden Processes

Theoretical Survey of the Potential Energy Surfaces Associated with the N⁺(³P,D) + C₂H₄Reactions in the Gas Phase