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Fingerprints of antiaromaticity in the negative ion (Li$_3$Al$_4$)$^-$, this species being realizable via a laser vaporization technique, are revealed by means of an \emph{ab initio} quantum-chemical investigation. First, the ground-state equilibrium geometry of this ion is predicted. Also, for the corresponding inhomogeneous electron liquid, the characteristics of the HOMO are studied, both for the square and the rectangular Al$_4$ geometry in two low-lying isomers of the negative ion. There is no particular sensitivity to the change in geometry of the Al$_4$ configuration. Therefore, we have calculated theoretically chemical shifts (NICS), which contain remarkable fingerprints of antiaromaticity. As to future directions, some comments are added in relation to the Shannon entropy., Comment: Phys. Chem. Liquids (to appear in vol. 52, 2014)

We have followed a "molecular" approach to study impurity effects in graphene. This is thought as the limiting case of an infinitely large cluster of benzene rings. Therefore, we study several carbon clusters, with increasing size, from phenalene, including three benzene rings, up to coronene 61, with 61 benzene rings. The impurities considered were a chemisorbed H atom, a vacancy, and a substitutional proton. We performed HF and UHF calculations using the STO-3G basis set. With increasing cluster size in the absence of impurities, we find a decreasing energy gap, here defined as the HOMO-LUMO difference. In the case of H chemisorption or a vacancy, the gap does not decrease appreciably, whereas it is substantially reduced in the case of a substitutional proton. The presence of an impurity invariably induces an increase of the density of states near the HOMO level. We find a zero mode only in the case of a substitutional proton. In agreement with experiments, we find that both the chemisorbed H, the substitutional proton, and the C atom near a vacancy acquire a magnetic moment. The relevance of graphene clusters for the design of novel electronic devices is also discussed., Comment: to appear in Phys. Lett. A

Krueger some years ago proposed a cluster LiBeBCNOF, now called periodane. His ground-state isomer proposal has recently been refined by Bera et al. using DFT. Here, we take the approach of molecules in such a cluster as starting point. We first study therefore the triangular molecule LiOB by coupled cluster theory (CCSD) and thereby specify accurately its equilibrium geometry in free space. The second fragment we consider is FBeCN, but treated now by restricted Hartree-Fock (RHF) theory. This four-center species is found to be linear, and the bond lengths are obtained from both RHF and CCSD calculations. Finally, we bring these two entities together and find that while LiOB remains largely intact, FBeCN becomes bent by the interaction with LiOB. Hartree-Fock and CCSD theories then predict precisely the same lowest isomer found by Bera et al. solely on the basis of DFT., Comment: to appear in Phys. Lett. A

Ab initio calculations including electron correlation are still extremely costly except for the smallest atoms and molecules. Therefore, our purpose in the present study is to employ a bond-order correlation approach to obtain, via equilibrium molecular energies, molecular dissociation energies and heats of formation for some 20 molecules containing C, H, and O atoms, with a maximum number of electrons around 40. Finally, basis set choice is shown to be important in the proposed procedure to include electron correlation effects in determining thermodynamic properties. With the optimum choice of basis set, the average percentage error for some 20 molecules is approximately 20% for heats of formation. For molecular dissociation energies the average error is much smaller: ~0.4., Comment: Mol. Phys., to be published

A crystalline form of LiBC is known which has been predicted to be superconducting, with a Tc comparable to that of MgB_2. In both compounds, superconductivity is enhanced by the presence of two electronic bands, one of which is close to a dimensional crossover. Here, we take a quantum chemical approach, and investigate the structural and electronic properties of small clusters (LiBC)_n (n=1-4). With increasing cluster size, we find that several properties of crystalline LiBC evolve naturally from the corresponding properties of the clusters. In particular, one may recognize the origin of the solid bilayered structure, typical of magnesium diboride, and the character of the electronic sigma-band, arising from the overlap of the atomic orbitals in the in-plane BC rings. Two aspects especially emphasized are (a) the HOMO-LUMO gap as function of n and (b) the role of different spin multiplicity., Comment: Phys. Lett. A, accepted

The present study of small molecules containing silicon has been motivated by (a) the considerable interest being shown currently in the kinetics and reactivity of such molecules, and (b) the biotechnological potential of silicon-derivate surfaces as substrates in the adsorption of, for instance, amino acids and proteins. Therefore, we have studied by (i) a semi-empirical approach and (ii) an ab initio procedure employing low-order Moller-Plesset perturbation theory, the molecular correlation energies of some neutral closed and open shell silicon-containing molecules in the series SiXnYm. Procedure (i) is shown to have particular merit for the correlation of the ionic members studied in the above series, while the ab initio procedures employed come into their own for neutral species., Comment: Mol. Phys., to be published

In a recent study by Kornath et al. [J. Chem. Phys. 118 (2003) 6957], the Li_n clusters with n=2, 4 and 8 have been isolated in argon matrices at 15 K and characterized by Raman spectroscopy. This has prompted us to carry out a theoretical study on such clusters up to n=10, using Hartree-Fock theory, plus low-order Moeller-Plesset perturbation corrections. To check against the above study of Kornath et al., as a by-product we have made the same approximations for n=6 and 8 as we have for n=10. This has led us to emphasize trends with n through the Li_n clusters for (i) ground-state energy, (ii) HOMO-LUMO energy gap, (iii) dissociation energy, and (iv) Hartree-Fock eigenvalue sum. The role of electron correlation in distinguishing between low-lying isomers is plainly crucial, and will need a combination of experiment and theory to obtain decisive results such as that of Kornath et al. for Li_8. In particular, it is shown that Hartree-Fock theory plus bond order correlations does account for the experimentally observed symmetry T_d symmetry for Li_8., Comment: accepted for publication in J. Chem. Phys

Motivated by solid-state studies on the cleavage force in Si, and the consequent stretching of chemical bonds, we here study bond stretching in the, as yet unsynthesized, free space molecule Si6H6. We address the question as to whether substantial bond stretching (but constrained to uniform scaling on all bonds) can result in a transition from ring current behaviour, characteristic say of benzene at its equilibrium geometry, to localized pi-electrons on Si atoms. Some calculations are also recorded on dissociation into 6 SiH radicals. While the main studies have been carried out by unrestricted Hartree-Fock (HF) theory, the influence of electron correlation has been examined using two forms of density functional theory. Planar Si6H6 treated by HF is bound to be unstable, not all vibrational frequencies being real. Some buckling is then allowed, which results in real frequencies and stability. Evidence is then provided that the non-planar structure, as the Si-Si distance is increased, exhibits pi-electron localization in the range 1.2-1.5 times the equilibrium distance.