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J Phys Chem B. 2008 Jan 17;112(2):520-8. Epub 2007 Dec 22.

Electronic structure of the acetonitrile and acetonitrile dimer anions: a topological investigation.

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Centre for Research in Molecular Modeling and Department of Chemistry & Biochemistry, Concordia University, Montréal, Québec H4B 1R6, Canada.


Acetonitrile molecules are known for their intriguing ability to accommodate an excess electron in either a diffuse dipole-bound orbital, away from the valence electrons, or in its valence orbitals, depending on the environment. In this work, we report a computational investigation of the monomer and dimer acetonitrile anions, with the main goal of gaining further insight into the unusual electronic structure of these species. To this end, the topology of the electron density distribution has been examined in detail with the quantum theory of atoms in molecules (AIM). The excess electron is found to affect the topology of the electron density very differently for two dipole-bound-electron isomers of the acetonitrile dimer anion: for the head-to-tail isomer, the electron density simply decays away from the atomic nuclei, and the presence of the excess electron only manifests itself in the Laplacian of the electron density as a very diffuse region of "dipole-bound" charge concentration; in contrast, for the "solvated-electron" head-to-head isomer, a maximum of electron density without a corresponding atomic nucleus is observed, which topologically corresponds to a pseudo-atom of electron density. The acetonitrile dimer appears to be the smallest solvent cluster anion to exhibit such a non-nuclear attractor due to the presence of a solvated electron. Although the "solvated-electron" isomer is thermodynamically less stable than the head-to-tail isomer at 0 K, its floppy nature leads to a higher vibrational entropy that makes it the most stable acetonitrile dimer, anionic or neutral, above 150 K. As for the acetonitrile dimer anion with a valence-bound electron, its structure is characterized by acetonitrile molecules connected to each other at the cyanide carbon atoms; the AIM analysis reveals that, although this C-C bond is relatively weak, with an estimated bond order of 0.6, it possesses genuine covalent character and is not a "pseudo-bond" as previously speculated. We also report the first multireference electronic structure calculations of the valence-bound-electron acetonitrile monomer and dimer anions, the highest-level calculations of these species to date. The acetonitrile radical anion is unstable in the gas phase and is topologically characterized by a radical-like nonbonded charge concentration located at the cyanide carbon atom. Based on the results of the AIM analysis, the previously proposed resonance description of the valence-bound-electron acetonitrile anion is refined, and a new resonance description of the dimer anion is proposed. Overall, this work demonstrates the rich topological variety of the excess electron interacting with acetonitrile molecules, which manifests itself as charge concentrations, pseudo-atoms, and covalent bonds.

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