Car-Parrinello density matrix search with a first principles fictitious electron mass method for electronic wave function optimization.
In spite of its success in molecular dynamics and the advantage of being a first order propagation technique, the Car-Parrinello method and its variations have not been successful in self-consistent-field (SCF) wave function optimization due to slow convergence. In this article, we introduce a first principles fictitious mass scheme to weigh each individual density element differently and instantaneously. As an alternative to diagonalization in SCF, the Car-Parrinello scheme is implemented as a density matrix search method. Not only does the fictitious mass scheme developed herein allow a very fast SCF convergence, but also the Car-Parrinello density matrix search (CP-DMS) exhibits linear scaling with respect to the system size for alanine helical chain test molecules. The excellent performance of CP-DMS holds even for very challenging compact three-dimensional quantum particles. While the conventional diagonalization based SCF method has difficulties optimizing electronic wave functions for CdSe quantum dots, CP-DMS shows both smooth and faster convergence.
Li
Xiaosong
X
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA. li@chem.washington.edu
Moss
Christopher L
CL
Liang
Wenkel
W
Feng
Yong
Y
D000409:Alanine / Q000737:chemistry; D019187:Cadmium Compounds / Q000737:chemistry; D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D045663:Quantum Dots; D011789:Quantum Theory; D018036:Selenium Compounds / Q000737:chemistry
D019187:Cadmium Compounds; D018036:Selenium Compounds; C058667:cadmium selenide; D000409:Alanine