Institut de Ciencia Molecular, Parc Científic, Universitat de València, Catedrático José Beltrán, 2. E-46980 València, Spain.
J Chem Phys. 2012 Sep 14;137(10):104102. doi: 10.1063/1.4747535.
A new multireference configuration interaction method using localised orbitals is proposed, in which a molecular system is divided into regions of unequal importance. The advantage of dealing with local orbitals, i.e., the possibility to neglect long range interaction is enhanced. Indeed, while in the zone of the molecule where the important phenomena occur, the interaction cut off may be as small as necessary to get relevant results, in the most part of the system it can be taken rather large, so that results of good quality may be obtained at a lower cost. The method is tested on several systems. In one of them, the definition of the various regions is not based on topological considerations, but on the nature, σ or π, of the localised orbitals, which puts in evidence the generality of the approach.
提出了一种新的使用局域轨道的多参考组态相互作用方法，其中将分子系统划分为不同重要性的区域。处理局域轨道的优势得到了增强，即可以忽略长程相互作用。实际上，虽然在分子中发生重要现象的区域中，相互作用的截止值可以小到足以得到相关的结果，但在系统的大部分区域中，可以取更大的值，从而以较低的成本获得高质量的结果。该方法在几个系统上进行了测试。其中之一是，各个区域的定义不是基于拓扑学考虑，而是基于局域轨道的性质，即 σ 或 π，这突出了该方法的通用性。
