Theoretical Study of RbOH, CsOH, FrOH, and Their Cations:  Geometries, Vibrational Frequencies, and the Ionization Energies

Lee, Edmond P. F.; Wright, Timothy G.

doi:10.1021/jp034747y

Cited by 16 publications

(12 citation statements)

References 38 publications

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“…We interpret this as an increasing ionicity of the MS species from LiS to CsS, but with a slight increase in covalency once FrS is reached. We have noted such a trend in the corresponding dioxides, 32 oxides, 17 and hydroxides 33 and attributed this covalency to overlap between the 6s and 6p orbitals of francium, and the p orbitals on oxygen; and a similar attribution is made here. We have noted that it is important to have basis functions that describe the n = 6 orbitals of francium, and that the corresponding molecular orbitals are explicitly included in any correlation treatment.…”

Section: F Ionization Energies and Heats Of Formationsupporting

confidence: 79%

Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations

Lee

Wright

2005

The Journal of Chemical Physics

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The heavier alkali-metal monosulfides ͑KS, RbS, CsS, and FrS͒ have been studied by high-level ab initio calculations. The RCCSD͑T͒ method has been employed, combined with large flexible valence basis sets. All-electron basis sets are used for potassium and sulfur, with effective core potentials being used for the other metals, describing the core electrons. Potential-energy curves are calculated for the lowest two neutral and cationic states: all neutral monosulfide species have a 2 ⌸ ground state, in contrast with the alkali-metal monoxide species, which undergo a change in the electronic ground state from 2 ⌸ to 2 ⌺ + as the group is descended. In the cases of KS, RbS, and CsS, spin-orbit curves are also calculated. We also calculate potential-energy curves for the lowest 3 ⌺ − and 3 ⌸ states of the cations. From the potential-energy curves, spectroscopic constants are derived, and for KS the spectroscopic results are compared to experimental spectroscopic values. Ionization energies, dissociation energies, and heats of formation are also calculated; for KS, we explore the effects of relativity and basis set extrapolation on these values.

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Section: F Ionization Energies and Heats Of Formationsupporting

confidence: 79%

Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations

Lee

Wright

2005

The Journal of Chemical Physics

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“…Then in 1994, Stiakaki et al 24 did a molecular orbital study and reported a Cs-OH bond distance of 2.447 Å. The latest work was done by Lee and Wright 25 in which they report the Cs-OH bond distance to be 2.635 Å with CCSD͑T͒ level of theory with LANL2͓9s8 p3d2 f ͔ basis set for Cs and aug-cc-pVTZ basis set for O and H. Although our DFT and MP2 results are rather different from the electron diffraction study by Girichev et al 26 and the latest ab initio study by Lee and Wright, 25 our results are very close to the earlier theoretical and experimental results, off only by 0.055 Å with B3LYP and 0.069 Å with MP2 compared to the microwave study 22 ͑see Table I͒. Nevertheless, for the purpose of this study, the difference in Cs-OH bond distance with the latest ab initio work is inconsequential as we are interested in relative change in the Cs-OH bond distance upon addition of water molecules.…”

Section: A Structures and Energeticscontrasting

confidence: 73%

Aqua dissociation nature of cesium hydroxide

Odde

Pak

Lee

et al. 2004

The Journal of Chemical Physics

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To understand the mechanism of aqueous base dissociation chemistry, the ionic dissociation of cesium-hydroxide in water clusters is examined using density functional theory and ab initio calculations. In this study, we report hydrated structures, stabilities, thermodynamic quantities, dissociation energies, infrared spectra, and electronic properties of CsOH(H(2)O)(n=0-4). With the addition of water molecules, the Cs-OH bond lengthened significantly from 2.46 A for n=1 to 3.08 A for n=4, which causes redshift in Cs-O stretching frequency. It is found that three water molecules are needed for the dissociation of Cs-OH, in contrast to the case of strong acid dissociation which requires at least four water molecules. However, the dissociation for n=3 could be considered as incomplete because a very weak CS em leader OH stretch mode is still present, while that for n=4 is complete since the Cs em leader OH mode no longer exists. This study can be related with hydration chemistry of cations and anions, and extended into the intra- and intercharge-transfer phenomena.

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“…1 Frequency calculations at the riv CCSD(T) level of theory using the QZ basis sets were performed for each optimized structure to identify whether the structure was a transition state or a local minimum of the potential energy surface. The final ground-state structure of the RbOH − ion is found to be linear, consistent with the ground-state structure of the neutral molecule [24,39]. Additionally the conformers OHRb − and ORbH − were also investigated and found to be transition states.…”

Section: Electronic Structure Calculationssupporting

confidence: 64%

Associative detachment of rubidium hydroxide

2013

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We performed calculations of the optimized structure, harmonic vibrational frequencies and dissociation energies of RbOH and its anion, and investigate the interactions between Rb and OH$^-$ leading to possible associative detachment pathways. The electron affinity of RbOH was computed to be 0.2890 eV, with a bond energy of Rb+OH$^-$ half that of Rb+OH. To determine other possible charge loss pathways, the Rb+OH and Rb+OH$^-$ dissociation curves were computed using couple cluster methods along all possible collisional angles. An adiabatic curve crossing between the neutral and charged molecule was found at the inner wall of the molecular potential curve for linear geometries. Associative detachment rates were estimated using the Langevin ion capture cross-section for hydroxide. We find for $v\ge 2$ an associative detachment rate of $>2\times 10^{-9}$ cm$^3$s$^{-1}$, while for $v=0$ and 1 no appreciable rate exists. This strong dependence on vibrational level suggests the ability to control the associative detachment rate directly

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Theoretical Study of RbOH, CsOH, FrOH, and Their Cations: Geometries, Vibrational Frequencies, and the Ionization Energies

Cited by 16 publications

References 38 publications

Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations

Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations

Aqua dissociation nature of cesium hydroxide

Associative detachment of rubidium hydroxide

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