New anionic states of the lithium trimer

Gutowski, Maciej; Simons, Jack

doi:10.1063/1.467408

Cited by 12 publications

(7 citation statements)

References 54 publications

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“…36 The Clanion only slightly perturbs the σ-aromatic HOMO in Li 3 Cl when compared to the isolated Li 3 + cation as can be seen in Figure 2. The σ-resonance energy in the Li 38 This value is appreciably lower than the IP ) 5.390 eV 39 of the Li atom and therefore the Li 3 radical can be considered as a superalkali. 40,41 According to our calculation, the Li 3 Cl molecule containing the superalkali Li 3 + cation is very stable and can be observed in the gas phase or in matrix isolation.…”

Section: σ-Aromatic and σ-Antiaromatic Triatomic Systemsmentioning

confidence: 85%

σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters

2003

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We extended the aromaticity concept to small σ-aromatic alkali metal and alkaline earth metal clusters. We performed ab initio calculations (B3LYP/6-311+G* and CCSD(T)/6-311+G*) on a selected group of triatomic and tetraatomic metal clusters. We have shown that the introduction of aromaticity and antiaromaticity in Li3 + and Li3 - ions, respectively, can be used to explain their relative stability and their structure. For the tetratomic 6σ-electron Li2Mg2 species we predicted that the cyclic σ-aromatic structures of Li2Mg2 are more stable than the classical linear Li−Mg−Mg−Li structure, thus showing the importance of the aromaticity in metal clusters. We believe that the further advancing of the aromaticity concept into metal clusters will be a useful tool in understanding chemical bonding in these species.

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Section: σ-Aromatic and σ-Antiaromatic Triatomic Systemsmentioning

confidence: 85%

σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters

2003

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“…However, they have been observed in another transition metal monoxide (FeO) . Recently, calculations have predicted excited triplet states for several cluster anions . The lowest excited state for CuO - would be to excite a 2pπ electron to the empty 4sσ orbital, giving a triplet excited state 3dδ 4 3dπ 4 3dσ 2 2pσ 2 2pπ 3 4sσ 1 ( 3 Π).…”

Section: Discussionmentioning

confidence: 99%

Chemical Bonding between Cu and OxygenCopper Oxides vs O₂ Complexes: A Study of CuO_x (x = 0−6) Species by Anion Photoelectron Spectroscopy

Wang

1997

J. Phys. Chem. A

134

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An extensive photoelectron spectroscopic study on the CuO x - (x = 0−6) species is presented. The photoelectron spectra of these species are obtained at four detachment photon energies: 2.33, 3.49, 4.66, and 6.42 eV. The spectra of the copper atom are included to show the dependence of the detachment cross sections on the photon energies. An intense two-electron transition to the 2P excited state of Cu is also observed in the 6.42 eV spectrum of Cu-. For CuO-, we observe an excited state of the anion, as well as photodetachment transitions to charge transfer excited states of CuO (Cu2+O2-). Six transitions are observed for CuO2 - at 6.42 eV, revealing all six valence molecular orbitals of the linear OCuO molecule. CuO3 - is observed to undergo photodissociation at 3.49 eV to give an internally hot CuO- plus O2. It is shown to have an OCuO2 type of structure, and its electronic structure can be viewed to be due to that of CuO perturbed by an O2. For CuO4 -, two isomers are observed. One of them undergoes photodissociation at 3.49 eV, and it is shown to be a Cu/O2 complex, Cu(O2)2 -. The second isomer yields spectra identical to that of the linear OCuO- with a slight energy shift and is concluded to be an OCuO- solvated by a very weakly bonded O2, (OCuO-)O2. CuO6 - is shown to exhibit similar behaviors as CuO4 - with a Cu/O2 complex, Cu(O2)3 -, and an O2-solvated CuO2 -, (OCuO-)(O2)2. The CuO5 - spectra are observed to be similar to that of CuO3 -, and it is shown to be due to a CuO3 - solvated by an O2, (OCuO2 -)O2.

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“…Very few anions possess bound excited electronic states, and the systems characterized to date are primarily atoms or diatomics. − In this contribution we study valence excited anionic states, in which an excess electron occupies a valence orbital of the neutral molecule, rather than dipole-bound anionic states, in which an extra electron is bound primarily due to the electrostatic interactions with the neutral molecule. − In the 90s Simons and Gutowski studied lithium-substituted double-Rydberg anions that possess a few bound valence anionic states. − These states, however, differ in multiplicity. In the present work, we address a molecular system with bound anionic states of the same spin multiplicity.…”

Section: Introductionmentioning

confidence: 99%

“…[4][5][6][7][8][9] In the 90s Simons and Gutowski studied lithium-substituted double-Rydberg anions that possess a few bound valence anionic states. [10][11][12] These states, however, differ in multiplicity. In the present work, we address a molecular system with bound anionic states of the same spin multiplicity.…”

Section: Introductionmentioning

confidence: 99%

Bound-Excited Electronic States of the Anion of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane

2003

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The doublet anionic states of 3,5,7,8, have been studied at the Hartree-Fock and the Møller-Plesset (MP) perturbation theory levels (up to fourth order) with aug(sp)-pVDZ basis sets. Our results indicate that TCNQ-F4 forms a stable anion of B 2g symmetry whose vertical electron attachment energy is 2.893 eV (at the MP4 level). In addition, we found two valence excited electronic states (2 2 B 3u and 1 2 A g ) of the anion that are stable vertically with respect to the neutral parent. The electronic stability of the third excited state (a core-excited 1 2 B 3u state) needs to be further investigated. We conclude that the neutral TCNQ-F4 at its equilibrium D 2h geometry may attach an excess electron to form any of these four states (i.e., 1 2 B 2g , 1 2 B 3u , 2 2 B 3u , and 1 2 A g ) and the corresponding MP4 vertical attachment energies (VAE) are 2.893, 0.822, 0.244, and 0.072 eV, respectively. However, due to second-order Jahn-Teller distortion, only the ground anionic state (1 2 B 2g ) possesses a minimum at D 2h symmetry. For the two valence excited states (2 2 B 3u and 1 2 A g ), negative curvatures cause out-of-plane deformations that lead to (i) an increase of the energy of the latter (1 2 A g ) state and (ii) achieving a minimumenergy structure of C 2 symmetry for the former where this state becomes a doublet A state and its vertical electronic stability increases to 2.721 eV.

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New anionic states of the lithium trimer

Cited by 12 publications

References 54 publications

σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters

σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters

Chemical Bonding between Cu and OxygenCopper Oxides vs O₂ Complexes: A Study of CuO_x (x = 0−6) Species by Anion Photoelectron Spectroscopy

Bound-Excited Electronic States of the Anion of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane

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New anionic states of the lithium trimer

Cited by 12 publications

References 54 publications

σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters

σ-Aromaticity and σ-Antiaromaticity in Alkali Metal and Alkaline Earth Metal Small Clusters

Chemical Bonding between Cu and OxygenCopper Oxides vs O2 Complexes: A Study of CuOx (x = 0−6) Species by Anion Photoelectron Spectroscopy

Bound-Excited Electronic States of the Anion of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane

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Chemical Bonding between Cu and OxygenCopper Oxides vs O₂ Complexes: A Study of CuO_x (x = 0−6) Species by Anion Photoelectron Spectroscopy