Siegbahn Per E M
Department of Physics, AlbaNova University Center, Stockholm University, 106 91 Stockholm, Sweden.
J Biol Inorg Chem. 2006 Sep;11(6):695-701. doi: 10.1007/s00775-006-0137-2. Epub 2006 Jul 8.
The accuracy of density functional theory with the B3LYP functional is reviewed for systems of relevance to transition-metal-containing enzymes. Calculated energies are commonly within 3-5 kcal/mol of the correct values; however, some exceptions have appeared in the literature and are discussed here. For example, the binding of NO and that of O(2) to metal centers have for some time been known to be underestimated. Most barriers for chemical reactions are overestimated except those involving hydrogen (or proton) transfer, which instead tend to be underestimated. A minor general improvement of the accuracy can probably be obtained by slightly reducing the amount of exact exchange in the B3LYP functional.
本文综述了含B3LYP泛函的密度泛函理论对于与含过渡金属酶相关体系的准确性。计算得到的能量通常与正确值相差在3 - 5千卡/摩尔以内；然而，文献中出现了一些例外情况，本文将对此进行讨论。例如，一氧化氮（NO）以及氧气（O₂）与金属中心的结合能一直以来都被低估。除了涉及氢（或质子）转移的反应外，大多数化学反应的势垒都被高估，而涉及氢（或质子）转移的反应势垒往往被低估。通过略微减少B3LYP泛函中精确交换的量，或许可以在一定程度上提高计算精度。
