An ab initio study of RbO, CsO and FrO (X2Î£+; A2Î ) and their cations (X3Î£â€“; A3Î )

Lee, Edmond P. F.; Lozeille, Jérôme; Soldán, Pavel; Daire, Sophia E.; Dyke, John M.; Wright, Timothy G.

doi:10.1039/b104835j

Cited by 50 publications

(45 citation statements)

References 27 publications

(7 reference statements)

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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 Formationmentioning

confidence: 77%

“…͑c͒ For Cs, the ECP46MWB ECP was employed, with the valence region being described by ͓10s8p5d4f3g͔ functions, described in full in Ref. 17. ͑d͒ For Fr, the CRENBL78 ECP was employed, with the valence region being described by ͓11s10p5d4f3g͔ functions, described in full in Ref.…”

Section: Theoretical Detailsmentioning

confidence: 99%

“…͑d͒ For Fr, the CRENBL78 ECP was employed, with the valence region being described by ͓11s10p5d4f3g͔ functions, described in full in Ref. 17.…”

Section: Theoretical Detailsmentioning

confidence: 99%

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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 Formationmentioning

confidence: 77%

Section: Theoretical Detailsmentioning

confidence: 99%

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

Lee

Wright

2005

The Journal of Chemical Physics

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“…[1]). We also note that for K + , Rb + and Cs + , a Alk þ D values were calculated [18] with the basis sets employed for those Alk + -Rg calculations [9], and good agreement with the values in Ref. [17] was obtained; c values were also reported, apparently for the first time.…”

Section: Resultsmentioning

confidence: 96%

Analysis of the bonding in alkali-cation/Rg complexes (Rg=He–Xe) using a simple model potential

2007

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“…Recently, we have performed a number of studies on these species, with reports on the thermodynamics and spectroscopy of LiO and LiO ϩ , 8 NaO, 9 and NaO ϩ , 9,10 the photoionization of NaO, 11 and in addition the spectroscopy and thermodynamics of RbO, CsO, and FrO and their cations. 12 These species are also of interest as, like other series of molecules, 13 there is a change in the symmetry of the ground state. For LiO ͑Refs.…”

Section: Introductionmentioning

confidence: 99%

What is the ground electronic state of KO?

Lee

Soldán

Wright

2002

The Journal of Chemical Physics

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High-level, restricted coupled cluster with singles, doubles, and perturbative triples calculations are performed to determine the ground electronic state of KO. In the absence of spin-orbit coupling, we find that the ground state is a 2 ⌺ ϩ state, with a 2 ⌸ state lying just over 200 cm Ϫ1 higher in energy. We ascertain that basis set extension, higher-order correlation energy, mass-velocity, and Darwin relativistic terms do not change this ordering. We then calculate the low-lying ⍀ states when spin-orbit coupling is turned on. The 2 ⌺ 1/2 ϩ state undergoes an avoided crossing with the 2 ⌸ 1/2 state, and we therefore designate the ground state as X 1 2 . This state is essentially 2 ⌺ 1/2 ϩ at short R, but essentially 2 ⌸ 1/2 at long R; there is a corresponding A 1 2 state with the opposite behavior. These states have significantly different shapes and so spectroscopy from the adiabatic states. Finally, we calculate the dissociation energy D 0 , of KO as 66Ϯ1 kcal mol Ϫ1 and derive ⌬H f (KO, 0 K) as 13.6Ϯ1 kcal mol Ϫ1 .

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An ab initio study of RbO, CsO and FrO (X2Î£+; A2Î ) and their cations (X3Î£â€“; A3Î )

Cited by 50 publications

References 27 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

Analysis of the bonding in alkali-cation/Rg complexes (Rg=He–Xe) using a simple model potential

What is the ground electronic state of KO?

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