Laser-induced fluorescence of CsH: The X1Σ+ state dissociation energy

Crépin, C.; Vergès, J.; Amiot, C.

doi:10.1016/0009-2614(84)87031-1

Cited by 17 publications

(2 citation statements)

References 13 publications

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“…At the QZ level, there is reasonably good agreement with available experimental data. [57][58][59][60][61][62][63][64][65][66][67][68][73][74][75][76][77] In the absence of experimental data for FrH and RaH, the present results can be compared to theoretical results of Koga et al, 22 which also used CCSD(T) with a DKH3 Hamiltonian. These NOSeC-CV-qzp results fall somewhere between the cc-pwCVTZ-DK and cc-pwCVQZ-DK values of the present work, suggesting that the NOSeC-CV sets also converge slowly towards the CBS limit, potentially overestimating r e and underestimating D e .…”

Section: Scalar Relativistic Effectsmentioning

confidence: 91%

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

Hill

Peterson

2017

The Journal of Chemical Physics

184

144

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The aug-cc-pVnZ-F12 basis set family: Correlation consistent basis sets for explicitly correlated benchmark calculations on anions and noncovalent complexes The Journal of Chemical Physics 147, 134106 (2017) (2006)], while the all-electron sets utilized second-order DKH Hamiltonians for 4s and 5s elements and third-order DKH for 6s and 7s. The accuracy of the basis sets is assessed through benchmark calculations at the coupled-cluster level of theory for both atomic and molecular properties. Not surprisingly, it is found that outer-core correlation is vital for accurate calculation of the thermodynamic and spectroscopic properties of diatomic molecules containing these elements.

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Section: Scalar Relativistic Effectsmentioning

confidence: 91%

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

Hill

Peterson

2017

The Journal of Chemical Physics

184

144

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“…In this work we investigate the important features of reaction 1 by using fluoromethane (CH 3 F) as a model HFC. The C−F and C−H bonds in CH 3 F are roughly the same strength (108 ± 3 and 101 ± 1 kcal/mol, respectively), and it should be pointed out that our focus on the activation of the C−F bond of CH 3 F does not imply that the C−H bond is not important. It means only that we admit the complexity of the problem and choose to treat the C−F activation aspects separately.…”

Section: Introductionmentioning

confidence: 99%

C−F Bond Activation by the 14-Electron M(X)(PH₃)₂ (M = Rh, Ir; X = CH₃, H, Cl) Complex. A Density Functional Study

Chu

1997

J. Am. Chem. Soc.

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The oxidative addition of the F−CH3 bond to coordinatively unsaturated trans-M(X)(PH3)2 (M = Rh, Ir; X = CH3, H, Cl) was theoretically investigated by density functional theory. All of the stationary points were determined at the B3LYP/LANL2DZ level. A configuration mixing model based on the theory of Pross and Shaik has been used to develop an explanation for the barrier height as well as the reaction enthalpy. Our theoretical findings suggest that the singlet−triplet splitting (ΔE st = E triplet − E singlet) of the ML3 species can be used as a basis to predict its reaction activity for oxidative additions; i.e., the smaller the ΔE st of ML3, the lower the barrier height and the larger the exothermicity, in turn, the faster the oxidative addition reaction. Considering the substituent effect, and the nature of the central metal, the following conclusions therefore emerge: for the 14-electron trans-M(X)(PH3)2 complex, a stronger π-donor ligand (such as Cl) as well as a heavier transition metal center (the third-row) will result in a smaller ΔE st, and thus will provide a potential model for the oxidative addition of saturated C−F bonds. In this work, an energetically feasible reaction mechanism which should not have radical intermediates involved is suggested.

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High‐Resolution Laser Techniques Applied To Reaction Dynamics

Vetter

1989

Israel Journal of Chemistry

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In this paper, using the particular case of the Cs(7P) + H2 → CsH + H reaction, it is shown how the application of high‐resolution continuous‐wave (CW) laser techniques to crossed‐beam experiments can yield information about the mechanism of reactive collisions. Firstly, CW laser techniques allow the preparation of Cs atoms in given fine and hyperfine structure levels; for this reaction, measurements of hyperfine cross‐sections vs. different orientations of the atomic orbital show how the molecular symmetry of the reagents controls the efficiency of the harpooning process involved. Secondly, the laser‐induced fluorescence (LIF) technique of detection allows the characterization of CsH products in given rotational levels. The high‐precision scanning of the CW laser frequency over absorption profiles of CsH molecules results in the determination of the Doppler shifts, which are associated with the recoil velocity of the products; two laser beam arrangements are used to provide the product velocity and angular scattering probability. A “forward” peaking is discovered, which depends on collision energy but not on product rotation. Finally, the technique of saturated absorption is applied for the first time to reactive experiments; it could lead to methods for selecting products which scatter in a given plane or in given directions.

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Laser-induced fluorescence of CsH: The X1Σ+ state dissociation energy

Cited by 17 publications

References 13 publications

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

C−F Bond Activation by the 14-Electron M(X)(PH₃)₂ (M = Rh, Ir; X = CH₃, H, Cl) Complex. A Density Functional Study

High‐Resolution Laser Techniques Applied To Reaction Dynamics

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Laser-induced fluorescence of CsH: The X1Σ+ state dissociation energy

Cited by 17 publications

References 13 publications

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K–Fr) and alkaline earth (Ca–Ra) elements

C−F Bond Activation by the 14-Electron M(X)(PH3)2 (M = Rh, Ir; X = CH3, H, Cl) Complex. A Density Functional Study

High‐Resolution Laser Techniques Applied To Reaction Dynamics

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Product

Resources

About

C−F Bond Activation by the 14-Electron M(X)(PH₃)₂ (M = Rh, Ir; X = CH₃, H, Cl) Complex. A Density Functional Study