Gaussian Basis Density Matrix Extended Lagrangian Ab ：基于高斯核密度矩阵扩展拉格朗日AB.pptVIP

Srinivasan S. Iyengar Department of Chemistry and Department of Physics, Indiana University Brief discussion of ab initio molecular dynamics Atom-centered Density Matrix Propagation (ADMP) Nut-n-bolts issues Some Results: Novel findings for protonated water clusters QM/MM generalizations: ion channels Gas phase reaction dynamics Molecular dynamics on a single potential surface Parameterized force fields (e.g. AMBER, CHARMM) Energy, forces: parameters obtained from experiment Molecular motion: Newton’s laws Works for large systems But hard to parameterize bond-breaking/formation (chemical reactions) Issues with polarization/charge transfer/dynamical effects Born-Oppenheimer (BO) Dynamics Solve electronic Schr?dinger eqn (DFT/HF/post-HF) for each nuclear structure Nuclei propagated using gradients of energy (forces) Works for bond-breaking but computationally expensive Large reactive, polarizable systems: Something like BO, but preferably less expensive. Extended Lagrangian dynamics Circumvent Computational Bottleneck of BO Avoid repeated SCF: electronic structure, not converged, but propagated “Simultaneous” propagation of electronic structure and nuclei: adjustment of time-scales Car-Parrinello (CP) method Orbitals expanded in plane waves Occupied orbital coefficients propagated O(N3) computational scaling (traditionally) O(N) with more recent Wannier representations (?) Atom-centered Density Matrix Propagation (ADMP) Atom-centered Gaussian basis functions Electronic Density Matrix propagated Asymptotic linear-scaling with system size Allows the use of accurate hybrid density functionals suitable for clusters Atom-centered Density Matrix Propagation (ADMP) Construct a classical phase-space {{R,V,M},{P,W,m}} The Lagrangian (= Kinetic minus Potential energy) Euler-Lagrange equations of motion for ADMP Equations of motion for density matrix and nuclei Nuclear Forces: What Really makes it work Density Matrix Forces: Use McWeeny Purified DM (3P2-2P3) in energy exp