Applications of Diatomics-in-Molecules Theory. II. Prediction of a Stable Li3 Molecule

Companion, Audrey L.; Steible, Daniel J.; Starshak, A. J.

doi:10.1063/1.1670645

Cited by 49 publications

(18 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although these experimental studies can provide detailed structural information, progress has been slowed by difficulties in making and correlating the measurements. The electronic structure of small metal clusters is under active study by a number of theoretical groups (20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37). Diverse methods from extended Huickel to ab initio calculations have been applied, leading to multifarious conclusions.…”

mentioning

confidence: 99%

Theoretical prediction of the vibrational spectra of group IB trimers

Richtsmeier

Gole

Dixon

1980

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

The molecular structures of the group IB trimers, Cu 3 , Ag 3 , and Au 3 , have been determined by using the semi-empirical diatomics-in-molecules theory. The trimers are found to have C 2v symmetry with bond angles between 65° and 80°. The trimers are bound with respect to dissociation to the asymptotic limit of an atom plus a diatom. The binding energies per atom for Cu 3 , Ag 3 , and Au 3 are 1.08, 0.75, and 1.16 eV, respectively. The vibrational frequencies of the trimers have been determined for comparison with experimental results. The vibrational frequencies are characterized by low values for the bending and asymmetric stretch modes. The frequency of the symmetric stretch of the trimer is higher than the stretching frequency of the corresponding diatomic. A detailed comparison of the theoretical results with the previously measured Raman spectra of matrix isolated Ag 3 is presented.

show abstract

mentioning

confidence: 99%

Theoretical prediction of the vibrational spectra of group IB trimers

Richtsmeier

Gole

Dixon

1980

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

show abstract

“…In all cases the stability of the potential well is remarkably insensitive to bending; bending to an interbond angle e = 90 ~ decreases the stability by less than 1 kcal mole -1. The contours for LiB, NaLi2 indicate a very slight increase in stability (~0-03 kcal mole -1) upon bending, which arises [2] from a minimum in the Manneback triplet curve [12]. Thus this feature may be an artifact of the triplet curve employed and is in any case very minor.…”

Section: Methodsmentioning

confidence: 88%

“…These are extended to large internuclear distances by the scaling procedure of Jen6 and Pliva [11]. For the triple t curve of Li e we use the calculation of Manneback [12] as quoted by Companion et al [2] which differs by no more than 1.1 kcal mole-t from the calculation of Wahl [13]. For NaLi the calculation of Bertoncini et al [14] is employed for both singlet and triplet curves.…”

Section: Methodsmentioning

confidence: 99%

“…Thus, there is considerable interest in the potential energy surfaces for these reactions, in order to help resolve the reaction dynamics. A diatomics-in-molecules calculation by Companion [2] for Lia, shows a triatomic molecule bound by ,,~ 9 kcal mole-lJ "= with respect to Li + Li 2. However, the reactive scattering studies also require a knowledge of unsymmetrical alkali trimers, M'M 2.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Semi-empirical potential energy surfaces for alkali atom-dimer exchange reactions

Whitehead

Grice

1973

Molecular Physics

View full text Add to dashboard Cite

Semi-empirical potential energy surfaces are calculated for the alkali atom-dimer exchange reactions of Li and Na. The surfaces exhibit a potential well at small internuclear distances which extends into the entrance and exit valleys without an energy barrier. The alkali triatomic complex is most stable in the linear or near-linear configuration; it remains stable however over all bent configurations. In the mixed alkali triatomic complex the configuration with the lighter alkali Li in the central position is the more stable; i.e. NaLiLi is more stable than LiNaLi and NaLiNa more stable than NaNaLi. The implications of these surfaces for the reaction dynamics of the alkali atom-dimer exchange reactions are briefly considered.

show abstract

“…Of these the pseudopotential calculations [2] predict Na3 and K3 to be slightly unstable with respect to the corresponding separated atom and dimer. Recent ab initio calculations [3] on Li3 suggest that linear Li3 is about 3 kcal/mol lower in energy than Li + Liz, whereas diatomics-in-molecule calculations [4] of Companion et al predict that it is bound by 9 kcal/mol with respect to the said reactants. Semiempirical calculations [ 51 of the potential-energy surfaces of the trimers involving Li and Na predict them to be stable molecules.…”

Section: Introductionmentioning

confidence: 97%

London potential‐energy surfaces for symmetrical alkali trimers

Mohammad

1978

Int J of Quantum Chemistry

View full text Add to dashboard Cite

AbstractsSemiempirical valence bond calculations have been performed on the symmetrical alkali trimers in order to obtain their potential-energy surface, binding energy, and equilibrium geometry. For these calculations original and generalized Rosen-Morse potentials for the ground state and two similar types of new potentials for the triplet state of alkali dimers have been used. At small internuclear distances the potential surfaces show a shallow well which extends into the entrance and exit valleys without an energy barrier. The trimers are found to be stable both in linear and bent configurations, but the most stable configuration in each case is linear and symmetric. The force constants corresponding to stretching and bending deformations of the trimers have been calculated for this configuration. It has been observed that unlike the stretching, the bending deformation does not sensitively affect the energy variation of the ground state of the trimers.Des calculs semi-empiriques ont t t t faits dans le cadre de l'approximation de la mtsomtrie pour les trimtres symitriques des mttaux alkalins, afin de trouver leurs surfaces d'tnergie potentielle, energies de liaisons et gtomttries d'tquilibre. Des potentiels de type Rosen-Morse pour M a t fondamental et deux types de potentiel semblables pour l'ttat triplet des dimeres ont t t t utilists. A des distances internucltaires faibles les surfaces de potentiel prtsentent un puits peu profond qui s'ttend dans les valltes d'entrte et de sortie sans barritre tnergitique. Les trimtres sont stables dans des configurations lintaires et dtformtes, mais dans tous les cas la configuration lintaire et symttrique est la plus stable. Les constantes de force correspondant aux dtformations angulaire et de valence des trim&res ont Ctt calcultes pour cette configuration. II s'avtre que l'tnergie de I'ttat fondamental des trimeres est moins sensiblei la deformation angulaire qu'8 celle de valence.Semi-empirische Valenzbindungsberechnungen sind fur die symmetrischen Alkalitrimere ausgefiihrt worden, um ihre Potentialenergieoberflachen, Bindungsenergien und Gleichgewichtsgeometrien zu erhalten. In diesen Berechnungen sind Rosen-Morse'sche Potentiale fur den Grundzustand und ahnliche Potentiale fur den Triplettzustand der Alkalidimere benutzt worden. An kleinen Kernabstanden haben die Potentialoberflachen einen seichten Topf, der in die Ein-und Ausgangstale ohne Energieschwelle ausgedehnt wird. Die Trimere sind sowohl in linearen als auch in deformierten Konfigurationen stabil. In allen Fallen ist aber die lineare, symmetrische Konfiguration die stabilste. Die den Dehnungs-und Deformationsschwingungen entsprechenden Kraftkonstanten der Trimere sind fur diese Konfiguration berechnet worden. Es zeigt sich, dass die Grundzustandsenergie der Trimere fur die Deformationsschwingung weniger empfindlich ist als fur die Dehnungsschwingung.

show abstract

Applications of Diatomics-in-Molecules Theory. II. Prediction of a Stable Li3 Molecule

Cited by 49 publications

References 15 publications

Theoretical prediction of the vibrational spectra of group IB trimers

Theoretical prediction of the vibrational spectra of group IB trimers

Semi-empirical potential energy surfaces for alkali atom-dimer exchange reactions

London potential‐energy surfaces for symmetrical alkali trimers

Contact Info

Product

Resources

About