The bonding in the low-lying states of MgO+2

Sodupe, Mariona; Bauschlicher, Charles W.

doi:10.1016/0009-2614(93)85390-a

Cited by 17 publications

(17 citation statements)

References 20 publications

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“…These MRCI values are in fair agreement with those of Sodupe and Bauschlicher [6], since differences between our and their values reach 77 cm À1 . However our x 2 is closer to the harmonic wavenumber in free O À 2 (1069 cm À1 ) confirming rather more the ionic character of the bonding in this molecule already pointed out by these authors.…”

Section: Spectroscopy Of Mgo þsupporting

confidence: 92%

“…Accordingly, the formation of the MgO bond in MgOO + is weakly disturbing the OO molecule. Therefore, this triatomic cation can be considered as Mg + ion interacting with a 'free' neutral diatomic O 2 molecule, in good accord with the earlier assumptions of Sodupe and Bauschlicher [6]. Fig.…”

Section: Equilibrium Structures Of Mgo þsupporting

confidence: 53%

“…However our R MgO distance for l-MgOO þ e X is larger by 0.2 bohr when compared to their value. Such differences are not surprising for this weakly bound charge quadrupole complex [6], where electronic correlation effects should be more critical for the description of their electronic wavefunctions. Finally, it is worth noticing that the OO equilibrium distance in the ground state of l-MgOO + is Table 1 Equilibrium geometries (R i , in bohr and angles in degrees), zero point vibrational energies (G 0 , in cm À1 ), rotational constants (A e , B e and C e ) vibration-rotation terms (a i , in cm À1 ) and harmonic (x i , in cm À1 ) and variationally determined anharmonic wavenumbers (m i , in cm À1 ) of the l-MgOO þ ð e X 4 R À Þ and MgO þ 2 ð e X 2 A2Þ states almost equal to the one of O 2 ðX 3 R À g Þ.…”

Section: Equilibrium Structures Of Mgo þmentioning

confidence: 88%

“…Sodupe and Bauschlicher [6] identified two stable isomers for MgO þ 2 : linear l-MgOO þ ð e X 4 R À Þ and bent MgO þ 2 ð e X 2 A 2 Þ. The doublet possesses a .…”

Section: Equilibrium Structures Of Mgo þmentioning

confidence: 98%

“…Upper limits for the bond dissociation energies are estimated for D 0 (MgO + -O) (63.75 ± 0.04 eV) and D 0 (Mg + -O 2 ) (61.13 ± 0.11 eV). Theoretically, the earlier work by Sodupe and Bauschlicher [6] at the VTZ/MCPF level and the more recent MP/ CBSQ computations by Jursic [7] were establishing that the ground state of MgO þ 2 is bent with a pronounced Mg 2þ O À 2 ionic character. In despite of its importance, very little information is available concerning the MgO þ 2 cation, its isomers, its electronic states and its reactivity.…”

Section: Introductionmentioning

confidence: 97%

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Electronic structure and spectroscopy of the cation

et al. 2008

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Section: Spectroscopy Of Mgo þsupporting

confidence: 92%

Section: Equilibrium Structures Of Mgo þsupporting

confidence: 53%

Section: Equilibrium Structures Of Mgo þmentioning

confidence: 88%

“…Sodupe and Bauschlicher [6] identified two stable isomers for MgO þ 2 : linear l-MgOO þ ð e X 4 R À Þ and bent MgO þ 2 ð e X 2 A 2 Þ. The doublet possesses a .…”

Section: Equilibrium Structures Of Mgo þmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 97%

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Electronic structure and spectroscopy of the cation

et al. 2008

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Preferential Activation of Primary CH Bonds in the Reactions of Small Alkanes with the Diatomic MgO^+. Cation

Schröder

Roithová

Alikhani

et al. 2010

Chemistry A European J

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The C-H bond activation of small alkanes by the gaseous MgO(+*) cation is probed by mass spectrometric means. In addition to H-atom abstraction from methane, the MgO(+*) cation reacts with ethane, propane, n- and iso-butane through several pathways, which can all be assigned to the occurrence of initial C-H bond activations. Specifically, the formal C-C bond cleavages observed are assigned to C-H bond activation as the first step, followed by cleavage of a beta-C-C bond concomitant with release of the corresponding alkyl radical. Kinetic modeling of the observed product distributions reveals a high preference of MgO(+*) for the attack of primary C-H bonds. This feature represents a notable distinction of the main-group metal oxide MgO(+*) from various transition-metal oxide cations, which show a clear preference for the attack of secondary C-H bonds. The results of complementary theoretical calculations indicate that the C-H bond activation of larger alkanes by the MgO(+*) cation is subject to pronounced kinetic control.

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Reactions of actinide ions with ethylene oxide

Gibson

2001

J. Mass Spectrom.

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Naked and oxo-ligated actinide (An) monopositive ions were reacted with ethylene oxide, cyclo-C(2)H(4)O (EtO). Along with An = U, Np, Pu and Am, ions of two lanthanide (Ln) elements, Ln = Tb and Tm, were studied for comparison. Metal and metal oxide ions, M(+), MO(+) and MO(2)(+), were generated by laser ablation and immediately reacted with EtO. Unreacted and product ions were detected by time-of-flight mass spectrometry. It was apparent that the overall reaction cross-sections decreased in the order U(+) > or = Np(+) > Pu(+) > Am(+). A primary reaction channel for each studied metal was the formation of MO(+) from M(+), in accord with the expected exothermicity of oxygen abstraction from EtO. For U, Np and Pu, the dioxides were also major products, indicating OAn(+)--O dissociation energies of at least 350 kJ mol(-1), the energy required for O-atom abstraction from EtO. For Am, Tb and Tm, the dioxides were only very minor products, reflecting the stabilities of the trivalent states and resistance to oxidation to higher valence states; the structures/bonding in these MO(2)(+) are intriguing given that the formal pentavalent bonding state is effectively unattainable. It was demonstrated that EtO, unlike more thermochemically favorable but kinetically restricted O-donors, is effective at achieving facile oxidation of actinide metal ions to the monoxide, and to the dioxide if the second O-abstraction reaction is exothermic. Several intriguing minor products were also identified, most of which incorporate metal--oxygen bonding and are attributed to the oxophilicity of the f-block elements; the contrast to the behavior of first-row d-block transition elements is striking in this regard. Particularly noteworthy was the formation of MH(4)(+) (and MOH(4)(+)), evidently via abstraction of all four H atoms from a single C(2)H(4)O molecule; the structures/bonding in these novel 'hydride' species are indeterminate and warrant further attention.

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The bonding in the low-lying states of MgO+2

Cited by 17 publications

References 20 publications

Electronic structure and spectroscopy of the cation

Electronic structure and spectroscopy of the cation

Preferential Activation of Primary CH Bonds in the Reactions of Small Alkanes with the Diatomic MgO^+. Cation

Reactions of actinide ions with ethylene oxide

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The bonding in the low-lying states of MgO+2

Cited by 17 publications

References 20 publications

Electronic structure and spectroscopy of the cation

Electronic structure and spectroscopy of the cation

Preferential Activation of Primary CH Bonds in the Reactions of Small Alkanes with the Diatomic MgO+. Cation

Reactions of actinide ions with ethylene oxide

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Product

Resources

About

Preferential Activation of Primary CH Bonds in the Reactions of Small Alkanes with the Diatomic MgO^+. Cation