Comparison of the widely used HF pseudo-potentials: MH+ (M = Fe, Ru, Os)

Leininger, Thierry; Riehl, Jean Frederic; Jeung, Gwang‐Hi; Pélissier, Maud

doi:10.1016/0009-2614(93)89246-e

Cited by 10 publications

(4 citation statements)

References 38 publications

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“…In another study, Leininger et al calculated the BDE of the OsH + ( 5 ) state using restricted Hartree-Fock multireference configuration interaction (RHF-MRCI) and multiconfiguration Hartree-Fock single and double configuration (MCHF-SDCI) levels of theory along with both small and large ECPs from Hay-Wadt, Christiansen and co-workers, and Stoll, Preuss, and co-workers. 37 For these various levels of theory and large core ECPs, their calculated 0 K BDEs had a range of 2.16-3.01 eV, whereas with small core ECPs, the 0 K BDEs had a range of 2.25-2.47 eV. The latter agree reasonably well with our experimental results.…”

Section: B Osh + Statessupporting

confidence: 84%

“…Our experimental results are in reasonable agreement with quantum chemical calculations performed here at the BHLYP and CCSD(T) level and in the literature. 30,37 The bond dissociation energy of the OsH + ground state is found to be larger than that for either the first-or second-row transition metal hydride cations FeH + and RuH + . This difference is a consequence of lanthanide contraction and relativistic effects, 80,88 which alter the relative size of the valence s and d orbitals and make s-dσ hybridization more effective.…”

Section: Discussionmentioning

confidence: 94%

“…Previous theoretical studies include all of the third-row transition-metal hydride cations. [30][31][32][33][34][35][36][37][38] We continue these studies here by reporting absolute cross sections as a function of kinetic energy for reactions of H 2 , D 2 , and HD with Os + and analyze them to acquire D 0 (Os + -H). Detailed theoretical calculations on the OsH + and OsH 2 + species were performed to assign electronic structures and explore possible mechanisms for these reactions.…”

Section: Introductionmentioning

confidence: 94%

“…There are currently no experimental results in the literature for OsH + , although theoretical studies for both OsH + and OsH 2 + have been published. 30,34,37 …”

Section: Introductionmentioning

confidence: 99%

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Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Hinton

Citir

Armentrout

2011

The Journal of Chemical Physics

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Reactions of the third-row transition metal cation Os(+) with H(2), D(2), and HD to form OsH(+) (OsD(+)) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os(+) in its (6)D (6s(1)5d(6)) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of OsH(+) and OsD(+) are analyzed to give a 0 K bond dissociation energy of D(0)(Os(+)-H) = 2.45 ± 0.10 eV. Quantum chemical calculations are performed here at several levels of theory, with B3LYP approaches generally overestimating the experimental bond energy whereas results obtained using BHLYP and CCSD(T), coupled-cluster with single, double, and perturbative triple excitations, levels show good agreement. Theory also provides the electronic structures of these species and the potential energy surfaces for reaction. Results from the reactions with HD provide insight into the reaction mechanism and indicate that Os(+) reacts via a direct reaction. We also compare this third-row transition metal system with the first-row and second-row congeners, Fe(+) and Ru(+), and find that Os(+) reacts more efficiently with dihydrogen, forming a stronger M(+)-H bond. These differences can be attributed to the lanthanide contraction and relativistic effects.

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Section: B Osh + Statessupporting

confidence: 84%

Section: Discussionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 94%

“…There are currently no experimental results in the literature for OsH + , although theoretical studies for both OsH + and OsH 2 + have been published. 30,34,37 …”

Section: Introductionmentioning

confidence: 99%

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Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Hinton

Citir

Armentrout

2011

The Journal of Chemical Physics

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Activation of Methane by Os⁺: Guided‐Ion‐Beam and Theoretical Studies

et al. 2013

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Activation of methane by the third‐row transition‐metal cation Os+ is studied experimentally by examining the kinetic energy dependence of reactions of Os+ with CH4 and CD4 using guided‐ion‐beam tandem mass spectrometry. A flow tube ion source produces Os+ in its electronic ground state and primarily in the ground spin–orbit level. Dehydrogenation to form [Os,C,2 H]++H2 is exothermic, efficient, and the only process observed at low energies for reaction of Os+ with methane, whereas OsH+ dominates the product spectrum at higher energies. The kinetic energy dependences of the cross sections for several endothermic reactions are analyzed to give 0 K bond dissociation energies (in eV) of D0(Os+C)=6.20±0.21, D0(Os+CH)=6.77±0.15, and D0(Os+CH3)=3.00±0.17. Because it is formed exothermically, D0(Os+CH2) must be greater than 4.71 eV, and a speculative interpretation suggests the exothermicity exceeds 0.6 eV. Quantum chemical calculations at the B3LYP/def2‐TZVPP level show reasonable agreement with the experimental bond energies and with previous theoretical values available. Theory also provides the electronic structures of the product species as well as intermediates and transition states along the reactive potential energy surfaces. Notably, the structure of the dehydrogenation product is predicted to be HOsCH+, rather than OsCH2+, in contrast to previous work.

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Evaluation of the Volume Effect in the Core–Core Interaction Energy for Alkali Diatomics

Jeung

1997

Journal of Molecular Spectroscopy

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Comparison of the widely used HF pseudo-potentials: MH+ (M = Fe, Ru, Os)

Cited by 10 publications

References 38 publications

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Activation of Methane by Os⁺: Guided‐Ion‐Beam and Theoretical Studies

Evaluation of the Volume Effect in the Core–Core Interaction Energy for Alkali Diatomics

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Comparison of the widely used HF pseudo-potentials: MH+ (M = Fe, Ru, Os)

Cited by 10 publications

References 38 publications

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD

Activation of Methane by Os+: Guided‐Ion‐Beam and Theoretical Studies

Evaluation of the Volume Effect in the Core–Core Interaction Energy for Alkali Diatomics

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Product

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Activation of Methane by Os⁺: Guided‐Ion‐Beam and Theoretical Studies