Ab Initio Molecular Dynamics with Dual Basis Set Methods
详细信息 查看全文
- 作者：Ryan P. Steele ; Martin Head-Gordon ; John C. Tully
- 刊名：Journal of Physical Chemistry A
- 出版年：2010
- 出版时间：November 4, 2010
- 年：2010
- 卷：114
- 期：43
- 页码：11853-11860
- 全文大小：226K
- 年卷期：v.114,no.43(November 4, 2010)
- ISSN：1520-5215
文摘
On-the-fly, ab initio classical molecular dynamics are demonstrated with an underlying dual basis set potential energy surface. Dual-basis self-consistent field (Hartree−Fock and density functional theory) and resolution-of-the-identity second-order Møller−Plesset perturbation theory (RI-MP2) dynamics are tested for small systems, including the water dimer. The resulting dynamics are shown to be faithful representations of their single-basis analogues for individual trajectories, as well as vibrational spectra. Computational cost savings of 58% are demonstrated for SCF methods, even relative to Fock-extrapolated dynamics, and savings are further increased to 71% with RI-MP2. Notably, these timings outperform an idealized estimate of extended-Lagrangian molecular dynamics. The method is subsequently demonstrated on the vibrational absorption spectrum of two NO+(H2O)3 isomers and is shown to recover the significant width of the shared-proton bands observed experimentally.