Unusual Inorganic Biradicals: A Theoretical Analysis
Journal Article
·
· Angewandte Chemie International Edition (Online)
Triatomic ions in the series FX2+, where X = O, S, Se, Te and Po are the terminal atoms, exhibit unusually high biradical characters (0.76 < β < 0.92), as measured from the analysis of Multi-Reference Configuration Interaction (MRCI) wavefunctions. Candidates in this series have the largest biradical character among the homologous, 18 valence electron CX22-, NX2-, X3 and OX2 (X = O, S, Se, Te and Po) systems. In the same scale the biradical character of ozone (O3) is just 0.19, whereas that of trimethylenemethane [C(CH2)3] is 0.97 (β=1 for an "ideal" biradical). For the 24 electron XO2 series, consisting of molecules with two oxygen atoms and a moiety X that is isoelectronic to oxygen, i.e. X= CH2, NH, O, F+, the singlet (S) state is lower than the triplet (T) one and the S-T splitting as well the barrier between their "open" and "ring" configurations was found to depend linearly with the inverse of the biradical character.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1083391
- Report Number(s):
- PNNL-SA-92775; KC0301020
- Journal Information:
- Angewandte Chemie International Edition (Online), Journal Name: Angewandte Chemie International Edition (Online) Journal Issue: 22 Vol. 52; ISSN 1521-3773
- Publisher:
- Gesselschaft Deutscher Chemiker
- Country of Publication:
- United States
- Language:
- English
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