Low-lying electronic states of InBi: a configuration interaction study

Chattopadhyay, Asis Kumar; Chattopadhyaya, Surya; Das, Kalyan Kumar

doi:10.1016/s0166-1280(03)00007-1

Cited by 4 publications

(5 citation statements)

References 46 publications

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“…Finally, in the same figure the Q el values for a number of group 13-group 15 isoelectronic diatomics with the intragroup 14 species are also included, as obtained by using thelevels reported in a series of theoretical papers based on the multireference single double configuration interaction ͑MRS-DCI͒ approach by Das and co-workers. [57][58][59][60][61][62][63][64][65] In Fig. 2, in accordance with the considerations made previously, the decrease in the partition function for the heavier molecules as a consequence of the increase of the spin-orbit splitting is quite apparent.…”

Section: Moleculesupporting

confidence: 89%

The dissociation energy of the new diatomic molecules SiPb and GePb

Ciccioli

Gigli

Meloni

et al. 2007

The Journal of Chemical Physics

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The diatomic molecules SiPb and GePb were for the first time identified by producing high temperature vapors of the constituent pure elements in a "double-oven-like" molecular-effusion assembly. The partial pressures of the atomic, heteronuclear, and homonuclear gaseous species observed in the vapor, namely, Si, Ge, Pb, SiPb, GePb, Pb2, Gen, and Sin (n=2-3), were mass-spectrometrically measured in the overall temperature ranges 1753-1961 K (Ge-Pb) and 1992-2314 K (Si-Pb). The dissociation energies of the new species were determined by second- and third-law analyses of both the direct dissociation reactions and isomolecular exchange reactions involving homonuclear molecules. The selected values of the dissociation energies at 0 K (D0 degrees) are 165.1+/-7.3 and 141.6+/-6.9 kJ/mol, respectively, for SiPb and GePb, and the corresponding enthalpies of formation (DeltafH0 degrees) are 476.4+/-7.3 and 419.3+/-6.9 kJ/mol. The ionization efficiency curves of the two species were measured, giving the following values for the first ionization energies: 7.0+/-0.2 eV (SiPb) and 7.1+/-0.2 eV (GePb). A computational study of the species SiPb and GePb was also carried out at the CCSD(T) level of theory using the relativistic electron core potential approach. Molecular parameters, adiabatic ionization energies, adiabatic electron affinities, and dissociation energies of the title species were calculated, as well as the enthalpy changes of the exchange reactions involving the other Pb-containing diatomics of group 14. Finally, a comparison between the experimental and theoretical results is presented, and from a semiempirical correlation the unknown dissociation energies of the SiSn and PbC molecules are predicted as 234+/-7 and 185+/-11 kJ/mol, respectively.

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Section: Moleculesupporting

confidence: 89%

The dissociation energy of the new diatomic molecules SiPb and GePb

Ciccioli

Gigli

Meloni

et al. 2007

The Journal of Chemical Physics

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“…For BiIn − , the first calculated transition to the neutral X 3 Σ − ground state of 1.85 eV matched the experimental value of 1.85 eV. Bands A, B, and C can be assigned to transitions to the 3 Π, 1 Δ, and 1 Π low lying neutral states of BiIn based on a configuration interaction (CI) study by Chattopadhyay et al Our calculated transition of band B at 2.69 eV agrees well with the experimental value of 2.63. Further, our calculated energy separation between the X 3 Σ − ground state, and the first accessible singlet state 1 Δ of 0.97 eV agrees well with the calculated CI value of 0.86 eV.…”

Section: Resultssupporting

confidence: 82%

Origins of Stability in Mixed Bismuth−Indium Clusters

et al. 2010

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The electronic structure and stability of neutral and negatively charged Bi x In y (x ) 1-4, y ) 1-6) clusters are investigated through anionic photoelectron spectroscopy employing magnetic bottle and photoelectron velocity map imaging experiments. Experimental and theoretical adiabatic and vertical detachment energies of the anionic species containing up to 4 Bi and 4 In atoms are deduced from first principles calculations. Among the Bi x In y series, many clusters are found to exhibit special stability in the mass spectra, exhibit a large gap between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO gap), and a large formation energy. This stability is rationalized by different mechanisms. Bi 2 Inis classified as a gas phase Zintl species despite only having three atoms, making it the smallest possible case. Bi 3 In 2 -, with 12 valence electrons and a closo structure in agreement with Wade's rule, is similar to Bi 3 Ga 2 -, a gas phase Zintl analogue of Sn 5 2-. Bi 4 Inand Bi 4 In 2 are both found to follow Wade's rule, indicating gas phase Zintl clusters. BiIn 3 is a cyclic planar molecule similar to BiGa 3 and BiAl 3 , all-metal aromatic systems, and BiIn 5 is a 20 electron closed shell Jellium species. Additionally, an even-odd oscillation of the HOMO-LUMO gaps, formation energies, and adiabatic electron affinities are found correlating with the open-shell/closedshell nature of the clusters.

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“…[30][31][32][33][34][35] Some of the SCF MOs are localized d orbitals of the constituting atoms, while there are orbitals of very high orbital energies which are discarded. Finally, the number of active orbitals for CI calculations are (37,20,20,7), (43,22,22,9), and (41, 21, 21, 8) for TlAs, TlSb, and TlBi molecules, respectively. The numbers in parentheses refer to A 1 , B 1 , B 2 , and A 2 symmetry orbitals.…”

Section: Computational Detailsmentioning

confidence: 99%

“…In recent years, the phosphide, arsenide, antimonide, and bismuthide molecules of gallium and indium have been theoretically studied by large-scale configuration interaction (CI) calculations. − However, similar diatomic molecules of thallium have not been studied at all. In this paper, for the first time, we report the electronic structure and spectroscopic properties of TlX (X = As, Sb, Bi) molecules.…”

Section: Introductionmentioning

confidence: 99%

Electronic States of TlX (X = As, Sb, Bi): A Configuration Interaction Study

Chattopadhyay

Das

2004

J. Phys. Chem. A

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Ab initio based relativistic configuration interaction (CI) calculations are carried out to study the electronic spectrum of TlX (X = As, Sb, Bi) molecules. Potential energy curves and spectroscopic constants of low-lying electronic states of these isomers have been computed. Dissociation energies of ground-state molecules are calculated and compared with the experimentally determined values. Effects of the spin−orbit coupling on the spectroscopic properties are studied. The zero-field splitting of the ground state of TlX has been estimated from the spin−orbit CI results. The heavier molecule, TlBi, has a stronger effect of the spin−orbit coupling. Many avoided crossings in the potential curves of Ω states of these isomers are reported. Dipole moments of the ground and lowest few bound states, such as 3Π,Σ+, 1Δ, and 1Π, of TlX have been calculated. Transition probabilities of dipole-allowed and spin-forbidden transitions of these molecules are computed. The radiative lifetimes of some of the excited 0+ states are also estimated.

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Low-lying electronic states of InBi: a configuration interaction study

Cited by 4 publications

References 46 publications

The dissociation energy of the new diatomic molecules SiPb and GePb

The dissociation energy of the new diatomic molecules SiPb and GePb

Origins of Stability in Mixed Bismuth−Indium Clusters

Electronic States of TlX (X = As, Sb, Bi): A Configuration Interaction Study

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