Analytical Energy Gradients for the Cluster-in-Molecule MP2 Method and Its Application to Geometry Optimizations of Large Systems

by Ni, Zhigang; Wang, Yuqi; Li, Wei; Pulay, Peter; Li, Shuhua

An efficient analytical energy gradient algorithm for the cluster-in-molecule (CIM) second order Moller-Plesset perturbation theory (MP2) method is presented. In our algorithm, the gradient contributions from the nonseparable term of the two-body density matrix on a given atom is extracted from calculations on a cluster constructed for this atom. The other terms in the CIM-MP2 energy gradient expression are evaluated by constructing the density matrices of the whole system with the contributions from all clusters constructed. For basis sets with diffuse functions, tight CIM parameters are necessary to obtain accurate gradients. Benchmark calculations show that the CIM-MP2 method can accurately reproduce the conventional MP2 gradients and geometries for larger systems. The optimized structure of a 174-atom oligopeptide using the CIM-MP2 method with the cc-pVDZ basis set is in good agreement with the corresponding crystal structure. The present CIM-MP2 gradient program can be used for optimizing the geometries of large systems with hundreds of atoms on ordinary workstations.

Journal
Journal of Chemical Theory and Computation
Volume
15
Issue
6
Year
2019
Start Page
3623
ISBN/ISSN
1549-9626; 1549-9618
DOI
10.1021/acs.jctc.9b00259