A stepwise atomic, valence-molecular, and full-molecular optimisation of the Hartree-Fock/Kohn-Sham energy

作     者：Jansik, Branislav Host, Stinne Johansson, Mikael P. Olsen, Jeppe Jorgensen, Poul Helgaker, Trygve 

作者机构：Aarhus Univ Dept Chem Lundbeck Fdn Ctr Theoret Chem DK-8000 Aarhus C Denmark Univ Oslo Dept Chem Ctr Theoret & Computat Chem N-0315 Oslo Norway 

出 版 物：《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 (Phys. Chem. Chem. Phys.)

年 卷 期：2009年第11卷第27期

页      面：5805-5813页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 0702[理学-物理学] 

基　　金：Lundbeck Foundation Norwegian Research Council [179568/V30] 

主　　题：information loss Optimization algorithms Energy sources Density matrix 

摘      要：A hierarchical optimisation strategy has been introduced for minimising the Hartree-Fock/Kohn-Sham energy, consisting of three levels (3L): an atom-in-a-molecule optimisation, a valence-basis molecular optimisation, and a full-basis molecular optimisation. The density matrix formed at one level is used as a starting density matrix at the next level with no loss of information. To ensure a fast and reliable convergence to a minimum, the augmented Roothaan-Hall (ARH) algorithm is used in both the valence-basis and full-basis molecular optimisations. The performance of the ARH-3L method is compared with standard optimisation algorithms. Both for efficiency and reliability, we recommend to use the ARH-3L algorithm.