Photoelectron Spectroscopy and Ab Initio Study of the Doubly-Antiaromatic B-6(2-) Dianion in the LiB6- Cluster
A metal-boron mixed cluster, LiB6-, was produced and characterized by photoelectron spectroscopy and ab initio calculations. A number of electronic transitions were observed and used to compare with theoretical calculations. An extensive search for the global minimum of LiB6- was carried out via an ab initio genetic algorithm technique. The pyramidal C2v (1A1) molecule was found to be the most stable at all levels of theory. The nearest low-lying isomer was found to be a triplet C2 (3B) structure, 9.2 kcal/mol higher in energy at the CCSD(T)/6-311+G(2df)//B3LYP/6-311+G* level. Comparison of calculated detachment transitions from LiB6- and the experimental photoelectron spectra confirmed the C2v pyramidal global minimum structure. Natural population calculation revealed that LiB6- is a charge-transfer complex, Li+B62-, in which Li+ and B62- interact in a primarily ionic manner. Analyses of the molecular orbitals and chemical bonding of B62- showed that the planar cluster is two-fold (- and -) antiaromatic, which can be viewed as the fusion of two aromatic B3- units.
- Research Organization:
- Pacific Northwest National Lab., Richland, WA (US), Environmental Molecular Sciences Laboratory (US)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 15016314
- Report Number(s):
- PNNL-SA-43762; JCPSA6; 3226; KP1301030; TRN: US200512%%348
- Journal Information:
- Journal of Chemical Physics, Vol. 122, Issue 5; Other Information: Art. No. 054313; PBD: 1 Feb 2005; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
On the Structure and Chemical Bonding of Si62- and Si62- in NaSi6- Upon Na+ Coordination
Cu3C4-: A New Sandwich Molecule with Two Revolving C22- Units