抄録
The MCD spectra of meso-triarylsubporphyrins show a sign anomaly which is correlated with the acceptor properties of the aryl substituent. From the spectra, magnetic moments of the excited states are determined. In the context of a simplified orbital model, the sign change is attributed to the quenching of the magnetic moment of the LUMO by acceptor orbitals of the substituent. The actual calculation of this moment presents a major challenge to computational methods. It is shown that wave function techniques based on CASSCF underestimate the covalency effects that are responsible for the quenching. In contrast, a CI method based on DFT orbitals yields excellent results, which fully support the orbital model.
本文言語 | English |
---|---|
ページ(範囲) | 3960-3967 |
ページ数 | 8 |
ジャーナル | Journal of Physical Chemistry A |
巻 | 116 |
号 | 15 |
DOI | |
出版ステータス | Published - 2012 4月 19 |
ASJC Scopus subject areas
- 物理化学および理論化学