Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstr 12, 53115, Bonn, Germany.
J Biol Inorg Chem. 2011 Aug;16(6):821-9. doi: 10.1007/s00775-011-0787-6. Epub 2011 May 5.
In this commentary the challenges faced in the application of wavefunction-based ab initio methods to (open-shell) transition metal complexes of (bio)inorganic interest are briefly touched on. Both single-reference and multireference methods are covered. It is stressed that the generation and nature of the reference wavefunction is a subject of major importance. How erroneous results can be easily obtained even with coupled-cluster theory is illustrated through the example of the septet-quintet separation in iron(IV)-oxo complexes. Second, the interplay between relativistic and correlation effects is important. This is demonstrated with coupled-cluster calculations on models for dinuclear copper active sites, where relativity has a major influence on the relative stabilities of the bis(μ-oxo) and side-on peroxo species.
在这篇评论中，简要探讨了在（生物）无机感兴趣的（开壳）过渡金属配合物中应用基于波函数的从头算方法所面临的挑战。涵盖了单参考和多参考方法。强调生成和参考波函数的性质是一个主要问题。通过铁(IV)-氧配合物中七重态-五重态分离的例子说明了即使使用耦合簇理论也很容易得到错误的结果。其次，相对论效应和相关效应之间的相互作用很重要。这通过双铜活性位点模型的耦合簇计算得到了证明，其中相对论对双（μ-氧）和侧过氧物种的相对稳定性有重大影响。
