Density functional study of the isomerisation of MOH (M=Be and Mg)

Jain, Seema; Rout, Chittaranjan; Rastogi, R. C.

doi:10.1016/s0009-2614(00)01175-1

Cited by 12 publications

(16 citation statements)

References 26 publications

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“…7 Alkaline-earth metal monohydroxide radicals have been studied extensively with both quantum chemical methods and experiment using optical spectroscopy. 8 They are thought to be abundant in atmospheres of oxygen-rich late-type stars, 9 have been detected in stellar atmospheres, 10 and may play a role in flame chemistry. 11,12 The interesting variation in the nature of the M-OH bond from Be (covalent), to Mg (mixed ionic-covalent) and to Ca (ionic) has prompted a number of theoretical studies in the past.…”

Section: Introductionmentioning

confidence: 99%

“…11,12 The interesting variation in the nature of the M-OH bond from Be (covalent), to Mg (mixed ionic-covalent) and to Ca (ionic) has prompted a number of theoretical studies in the past. 10,13 The earliest investigation of a reaction between an alkaline earth metal oxide cation and water was conducted by Fehsenfeld and co-workers in their flowing-afterglow study. 14 Magnesium oxide cations reacted with heavy water to produce MgOD + and OD in helium buffer gas at a pressure B0.…”

Section: Introductionmentioning

confidence: 99%

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Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

Božović

Böhme

2009

Phys. Chem. Chem. Phys.

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Experimental investigations are reported for reactions of MO (+) (M = Ca, Sr, and Ba) with elemental hydrides water, ammonia and methane proceeding in the gas phase at 295 +/- 3 K in helium buffer gas at a pressure of 0.35 +/- 0.01 Torr. Measurements were taken with an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer and a novel electrospray ion source/ion selection quadrupole/selected-ion flow tube/triple quadrupole (ESI/qQ/SIFT/QqQ) mass spectrometer. All three alkaline-earth metal oxide ions exclusively abstract a H-atom from the three hydrides with rate coefficients > 1 x 10(-11) cm(3) molecule(-1) s(-1). Formation of metal hydroxide ion was followed by sequential addition of water or ammonia, but not methane. Density functional calculations have provided potential energy surfaces for the X-H bond activations leading to H-atom abstraction as well as those for O-atom transfer and H(2)O elimination (with ammonia and methane). A comparison of experimental and theoretical isotope effects points toward a mechanism involving the direct atom transfer from XH and XD to O in MO (+)via a three-centered transition structure.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

Božović

Böhme

2009

Phys. Chem. Chem. Phys.

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“…1) . This bent structure M1 is not the previous B3PW91 [5] calculations predicted bent structure for the geometries of the two bent structures were much different. Three bent transition states TS1, TS2, and TS3 ( Fig.…”

Section: Geometries For Stationary Pointsmentioning

confidence: 47%

“…However, we noted that the previous B3PW91 [5] calculations predicted that the ground-state HOMg should be a first-order saddle point and there should be a bent structure. We tried our best to carry out CASSCF geometry optimization calculations to search the mentioned bent structure on the ground-state PES of HOMg.…”

Section: Geometries For Stationary Pointsmentioning

confidence: 65%

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CASPT2 study on low‐lying states of HMgO and HOMg

Geng

Pei

et al. 2011

Int J of Quantum Chemistry

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The HMgO and magnesium monohydroxide (HOMg) have been reinvestigated using the complete active space self-consistent field (CASSCF) and multiconfiguration second-order perturbation theory (CASPT2) methods with the contracted atomic natural orbital (ANO) basis sets. The geometries of all stationary points along the potential energy surfaces (PESs) were optimized at the CASSCF/ANO levels. The ground and the first excited states of HMgO are predicted to be X

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C−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV₃O₁₀⁻ and FeV₅O₁₅⁻: A Comparison with Scandium‐Vanadium Oxide Clusters

et al. 2023

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Late transition metal‐bonded atomic oxygen radicals (LTM−O⋅−) have been frequently proposed as important active sites to selectively activate and transform inert alkane molecules. However, it is extremely challenging to characterize the LTM−O⋅−‐mediated elementary reactions for clarifying the underlying mechanisms limited by the low activity of LTM−O⋅− radicals that is inaccessible by the traditional experimental methods. Herein, benefiting from our newly‐designed ship‐lock type reactor, the reactivity of iron‐vanadium bimetallic oxide cluster anions FeV3O10− and FeV5O15− featuring with Fe−O⋅− radicals to abstract a hydrogen atom from C2−C4 alkanes has been experimentally characterized at 298 K, and the rate constants are determined in the orders of magnitude of 10−14 to 10−16 cm3 molecule−1 s−1, which are four orders of magnitude slower than the values of counterpart ScV3O10− and ScV5O15− clusters bearing Sc−O⋅− radicals. Theoretical results reveal that the rearrangements of the electronic and geometric structures during the reaction process function to modulate the activity of Fe−O⋅−. This study not only quantitatively characterizes the elementary reactions of LTM−O⋅− radicals with alkanes, but also provides new insights into structure‐activity relationship of M−O⋅− radicals.

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Density functional study of the isomerisation of MOH (M=Be and Mg)

Cited by 12 publications

References 26 publications

Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

CASPT2 study on low‐lying states of HMgO and HOMg

C−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV₃O₁₀⁻ and FeV₅O₁₅⁻: A Comparison with Scandium‐Vanadium Oxide Clusters

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Density functional study of the isomerisation of MOH (M=Be and Mg)

Cited by 12 publications

References 26 publications

Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

Activation of X–H and X–D bonds (X = O, N, C) by alkaline-earth metal monoxide cations: experiment and theory

CASPT2 study on low‐lying states of HMgO and HOMg

C−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV3O10− and FeV5O15−: A Comparison with Scandium‐Vanadium Oxide Clusters

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Product

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C−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV₃O₁₀⁻ and FeV₅O₁₅⁻: A Comparison with Scandium‐Vanadium Oxide Clusters