The odd–even alternation of heteroatom-doped carbon clusters AuCn− (n ⩽ 12): Experimental observations and density functional studies
✍ Scribed by Qin Zhang; Ling-chun Song; Xin Lu; Rong-bin Huang; Lan-Sun Zheng
- Publisher
- Elsevier Science
- Year
- 2010
- Tongue
- English
- Weight
- 614 KB
- Volume
- 967
- Category
- Article
- ISSN
- 0022-2860
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✦ Synopsis
Heteroatom-doped carbon cluster Odd-even alternation Time-of-flight mass spectrum Theoretical calculations a b s t r a c t A series of AuC n À clusters were generated by laser vaporization on time-of-flight mass spectrometer and the abundance of AuC n À display odd-even alternation with even-n clusters being relatively more abundant. Density functional studies at B3LYP level reveal that even-n AuC n À clusters adopt a 1 R ground state with a linear geometry for n = 2, and a 1 A 0 ground state with bent chain geometries for n = 4, 6, 8, 10, and 12. The geometric change from linear geometry of AuC 2 À to bent geometry of AuC n À (n = 4, 6, 8, 10, 12) is rationalized by the Mulliken-Walsh model. On the other hand, the odd-n AuC n À clusters adopt bent chain geometries in 1 A 0 ground states for n = 3 and 5, and in 3 A 00 ground state for n = 7, 9, and 11, as well as 3 R ground state for n = 1. This irregular stability is dependent on the energy gap between HOMO and LUMO.
After combination of even-n and odd-n AuC n À , the calculated incremental energy and vertical detachment energy (VDE) demonstrate that even-n AuC n À are more stable than neighboring odd-n ones, which is in agreement with the observed odd-even alternation of the TOF signal intensities.