New rovibrational data for MgOH and MgOD and the internuclear potential function of the ground electronic state

Bunker, P. R.; Kolbuszewski, Marcin; Jensen, Per; Brumm, Martin; Anderson, M. A.; Barclay, W. L.; Ziurys, L. M.; Ni, Yong Nian; Harris, David O.

doi:10.1016/0009-2614(95)00479-n

Cited by 33 publications

(23 citation statements)

References 7 publications

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“…For MgOH the potential energy function and rovibrational levels have been determined recently 4 and the recent study as well as previous calculations 2,3 show that the ground state of MgOH is linear but with a very flat bending potential. The analysis of the high-resolution gas-phase laser excitation spectra of MgOH showed that the A state is bent with a barrier of about 1970 cm Ϫ1 , and is considered to be the lower Renner-Teller component originating from a 2 ⌸ state.…”

Section: Introductionmentioning

confidence: 52%

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Ab initio calculations on the ground and excited states of BeOH and MgOH

Theodorakopoulos

Petsalakis

Hamilton

1999

The Journal of Chemical Physics

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Ab initio configuration interaction calculations have been carried out on the ground and excited electronic states of the BeOH and MgOH molecules as well as of the cations BeOH ϩ and MgOH ϩ , for linear and bent geometries. The excited states of the above molecules have not previously been calculated and experimental information exists only for the A -X system in MgOH and MgOD. The present results show that in the excited states the molecules MgOH and BeOH have similar M-O (MϭMg,Be) stretching and bending potentials. In general, the stretching potentials are rather complicated, showing a number of avoided crossings. Furthermore, most of the excited states show minima at R near R min of the corresponding cations BeOH ϩ and MgOH ϩ , indicating Rydberg contributions to the molecular excited states. The first excited state in both BeOH and MgOH is 2 2 AЈ, which along with 1 2 AЉ, forms the 1 2 ⌸ state of linear geometries and which in both systems has minimum energy at a bent geometry with bond angle near 115°. In MgOH, the 2 2 AЈ state is the A state of the observed A -X spectra and the theoretical transition energy and the barrier to linearity are in good agreement with the corresponding experimental quantities. Analogous spectra for BeOH, not reported as yet, would be expected on the basis of the present calculations at higher energies than the MgOH spectra by 0.6 eV. The results on the molecular ground-state potentials are similar to those of previous calculations, showing a linear minimum geometry for MgOH but with a very shallow bending potential, and for BeOH a bent minimum but with only a 50 cm Ϫ1 barrier to linearity.

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Section: Introductionmentioning

confidence: 52%

“…As mentioned in the Introduction, the ground state of MgOH has been previously treated in detail, including calculation of the potential energy function and rovibrational levels. 4 Thus, it shall not be dealt with any further in the present work.…”

Section: B Results Of the Calculations On Mgohmentioning

confidence: 99%

Ab initio calculations on the ground and excited states of BeOH and MgOH

Theodorakopoulos

Petsalakis

Hamilton

1999

The Journal of Chemical Physics

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“…31 The bond-length discrepancies are related to limitations in both basis sets and theoretical method. The use of larger basis sets somewhat improves the agreement with experiment: R(Mg-O) ) 1.778 Å for MgO and R(Mg-O) ) 1.781 Å for MgOH, both at QCISD/6-311++G(2df,2pd); however, we can not use such extended basis sets for the larger systems, so we restrict our analogies to data obtained with the more modest bases.…”

Section: Comparing Interactions Of Mg N O N and Lif With H And LI Atomentioning

confidence: 99%

Why Are (MgO)_n Clusters and Crystalline MgO So Reactive?

Boldyrev

Simons

1996

J. Phys. Chem.

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The electronic structures and chemical reactivities (toward H, Li, Li 2 , and H 2 ) are examined for small (MgO) n clusters. It is postulated that decreases in the clusters' reactivity toward the above prototypical species as the cluster size (n) increases is related to the decrease in valence unsaturation that accompanies increases in n. Further, it is suggested that the known high reactivity of MgO powder and crystal is likely related to surface or defect sites that possess high levels of valence unsaturation.

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“…If the metal-oxygen bond is highly ionic the molecule is linear, but if the bonding is more covalent the molecule is quasi-linear or nonlinear. For example, the heavier alkaline earth monohydroxides are definitely linear (1), though the slightly less ionic MgOH has a flat-bottomed bending potential function (12). AlOH is described as quasi-linear (13), the more covalent InOH has a bond angle of 132° (14), with a low barrier to linearity, and the mostly covalent CuOH has a bond angle of 110° (7), only slightly larger than the HOH angle in water itself.…”

Section: Introductionmentioning

confidence: 98%