The negative ion BN−and its role in determining the ground state of BN via photodetachment. An MRDCI ab initio study

Mawhinney, Robert C.; Bruna, Pablo J.; Grein, Friedrich

doi:10.1139/v93-198

Cited by 15 publications

(7 citation statements)

References 30 publications

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“…All studies (carried out with double-to quintuple-zeta basis sets and extended CI expansions) place the triplet slightly below the singlet state, from 0.02 to 0.10 eV [12,13,17,181. According to the best estimates, 1'Z' lies only 0.02-0.03 eV higher than 13H.…”

Section: Nature Of the Ground State Of Bnmentioning

confidence: 99%

Stability of BN and its ions, from BN3+ to BN2?: AN ab initioMRD-CI study

Bruna¹,

Mawhinney²,

Grein³

1995

Int. J. Quantum Chem.

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mThe stabilities of BN and its ions, from BN3+ to BN2-, were investigated by ab initio methods. Theory predicts the ground state of BN to be X3n, with a'Z + lying about 0.03 eV higher. Photodetachment of BN-and photoionization of BN are proposed as alternative routes to optical spectroscopy for identifying the ground state of BN. The electronic spectra of BN-and BN+ exhibit features similar to those observed for the isoelectronic C, ions. BN-and BN+ have low infrared intensities, whereas BN(X3H) is practically infrared-inactive. Fourteen electronic states of BN2+ and three of BN3+ are metastable, an uncommonly large number for multiply charged cations from the first row. Both high-energy ions might be characterized experimentally by the calculated ionization potentials and kinetic energy releases. In the gas phase, the dianion BN2-autodetaches spontaneously into BN-+ e-, but it could be stabilized, eg., in Li,BN crystals. 0 1995 John Wiley & Sons, Inc.

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Section: Nature Of the Ground State Of Bnmentioning

confidence: 99%

Stability of BN and its ions, from BN3+ to BN2?: AN ab initioMRD-CI study

Bruna¹,

Mawhinney²,

Grein³

1995

Int. J. Quantum Chem.

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“…The lowest state of B ϩ ϩN ϩ lies 27.39 eV above X 3 ⌸͑BN͒, using the experimental values for IP͑B͒ of 8.30 eV, IP͑N͒ of 14.54 eV, and a best theoretical estimate of 4.55 eV for D e ͑X 3 ⌸͒ of BN. 11 Table II gives energies of the repulsive channels B ϩ ϩN ϩ , labeled I-VII, as well as of the higher-lying attractive channels B 2ϩ ϩN, labeled a-f. Since both types of products are separated by at least 10 eV, the dication BN 2ϩ cannot have truly bound but quasibound ͑or metastable͒ states only.…”

Section: Atomic Energies Dissociation Channels and Correlatingmentioning

confidence: 99%

“…III͒, and ͑c͒ the best estimates of the dissociation energy D e of BN ͑X 3 ⌸͒, BN (a 1 ⌺ ϩ ), and BN ϩ ͑X 4 ⌺ Ϫ ͒, i.e., 4.55, 6.90, and 1.36 eV, respectively. 11,33 Zero point corrections are not included.…”

Section: Ionization Potentials and Ker Datamentioning

confidence: 99%

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Multireference configuration interaction studies on metastable states of the dication BN2+

Mawhinney

Bruna

Grein

1995

The Journal of Chemical Physics

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A multireference configuration interaction study of the hyperfine structure of the molecules CCO, CNN, and NCN in their triplet ground states Multireference CI calculations predict fourteen states of BN 2ϩ to be quasibound, an uncommonly large number for a first-row diatomic, confirming the important role played by the electropositive B atom in stabilizing molecular dications. About two-thirds of the metastable potentials have dissociation barriers ͑D eff ͒ between 0.59 and 2.25 eV, accommodating several vibrational levels and therefore being kinetically stable. The ground state X 3 ⌺ Ϫ , however, might be difficult to study experimentally because it is only weakly bound ͑D eff ϭ0.23 eV͒, and its formation via ionization of BN or BN ϩ has unfavorable Franck-Condon factors ͑FCF͒. The 1 5 ⌺ Ϫ state is the best candidate for detecting BN 2ϩ : Its barrier is the highest ͑D eff ϭ2.25 eV͒, sustaining about 30 vibrational levels ͑with tunneling lifetimes T Ϸϱ for Ͻ20͒, and the ionization FCFs are favorable. The 1 1 ⌬ state might also be detectable since its properties are similar to those of 1 5 ⌺ Ϫ . Near equilibrium, most metastable states are described by the configurations 3 2 451 2 and 3 2 41 3 , both having charge distributions B 2ϩ N. The adiabatic ionization potential into BN 2ϩ ͑X 3 ⌺ Ϫ ͒ is 21.4 eV for ionization from BN ϩ ͑X 4 ⌺ Ϫ ͒ and 32.9 eV from BN͑X 3 ⌸͒. The corresponding IPs into 1 5 ⌺ Ϫ lie 1.12 eV higher.

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“…There are a number of ab initio calculations available for The BN molecule was first observed by Douglas and the spectroscopic properties of BN (9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24). These studies Herzberg (3) who reported the analysis of a 3 P i -3 P i transipredict a 3 P ground state.…”

Section: Introductionmentioning

confidence: 99%