Structure of the Alkali Hydroxides. I. Microwave Spectrum of Gaseous CsOH

Lide, David R.; Kuczkowski, Robert L.

doi:10.1063/1.1840634

Cited by 82 publications

(43 citation statements)

References 13 publications

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“…The theoretical w e values are probably the most accurate available. For CsOH we agree with the rather uncertain gas phase value [106]. However, our results imply that all of the ui e values derived from matrix isolation studies [102.104,107] are systematically low.…”

Section: Alkali Hvdroxidessupporting

confidence: 77%

Theoretical Dissociation Energies for Ionic Molecules

Langhoff

Bauschlicher

Partridge

1985

Comparison of Ab Initio Quantum Chemistry With Experiment for Small Molecules

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Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters (D e , r e , u e ) for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended gaussian basis sets of at least triple-zeta plus double polarization quality are employed for the triatomic systems. By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials. With this model, correlation effects are relatively small (0.0-0.3 eV), but invariably increase D 0 . The importance of correlating the electrons on both the anion and the metal is discussed.The theoretical dissociation energies (D 0 ) are critically compared with the literature to rule out disparate experimental values. The theoretical studies combined with the experimental literature allow us to recommend D 0 values that are accurate to 0.1 eV for all systems considered. The systematic treatment of many different systems reveal many trends. For example, the dissociation energies of the alkali and alkaline-earth hydroxides are observed to be less than the corresponding fluorides by just slightly less than the difference in electron affinities of F and OH. In general, there is a strong correlation between the dissociation energy (to ions) and r e , because the bonding is predominantly electrostatic in origin.

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Section: Alkali Hvdroxidessupporting

confidence: 77%

Theoretical Dissociation Energies for Ionic Molecules

Langhoff

Bauschlicher

Partridge

1985

Comparison of Ab Initio Quantum Chemistry With Experiment for Small Molecules

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“…A strong spectrum of YC 2 was found near 775 nm (19), and another spectrum with many of the features expected for YCH was found in the 500 -600 nm region. However, no change occurs in this spectrum when CD 4 is used instead of CH 4 , which indicates either that the carrier contains no hydrogen or that it is not derived from methane. The spectrum increases in intensity by a factor of about 4 when water vapor is used instead of methane, suggesting that the carrier is YOH rather than YCH.…”

Section: Introductionmentioning

confidence: 87%

Electronic Spectra of YOH and YOD in the Visible Region: Strong Vibronic Coupling between the B1Π and C1Σ+ States

Adam¹,

Athanassenas²,

Gillett³

et al. 1999

Journal of Molecular Spectroscopy

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“…Neutral alkali and alkaline earth hydroxides (MOH) have been extensively studied both theoretically [10][11][12][13][14][15][16][17][18][19][20] and experimentally [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] (see also the reviews of A.Ellis 36 and Gurvitch et al 37 ). The interest lies in the general context of molecular structure and the understanding of the M-O bond.…”

Section: Introductionmentioning

confidence: 99%

Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH−

Kas

Loreau

Liévin

et al. 2017

The Journal of Chemical Physics

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We have performed a systematic ab initio study on alkali and alkaline earth hydroxide neutral (MOH) and anionic (MOH − ) species where M = Li, Na, K, Rb, Cs or Be, Mg, Ca, Sr, Ba. The CCSD(T) method using extended basis sets and MDF electron core potentials as been used to study their equilibrium geometries, interaction energies, adiabatic electron affinities and potential energy surfaces. All neutral and anionic species exhibit a linear shape with the exception of BeOH, BeOH − and MgOH − , for which the equilibrium structure is bent. In the context of sympathetic cooling of OH − by collision with ultracold alkali and alkaline earth atoms, we investigate the M-OH − potential energy surfaces and the associative detachment reaction M+OH − → MOH+e − , which is the only energetically allowed reactive channel in the cold regime. We discuss the implication for the sympathetic cooling of OH − and conclude than Li and K are the best candidates for ultracold buffer gas.

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Structure of the Alkali Hydroxides. I. Microwave Spectrum of Gaseous CsOH

Cited by 82 publications

References 13 publications

Theoretical Dissociation Energies for Ionic Molecules

Theoretical Dissociation Energies for Ionic Molecules

Electronic Spectra of YOH and YOD in the Visible Region: Strong Vibronic Coupling between the B1Π and C1Σ+ States

Ab initio study of the neutral and anionic alkali and alkaline earth hydroxides: Electronic structure and prospects for sympathetic cooling of OH−

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