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Efficiently Capturing Weak Interactions in ab Initio Molecular Dynamics with on-the-Fly Basis Set Extrapolation.
J Chem Theory Comput ; 14(11): 5535-5552, 2018 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-30335374
ABSTRACT
Weak interactions have a critical role in accurately portraying conformational change. However, the computational study of these often requires large basis electronic structure calculations that are generally cost-prohibitive within ab initio molecular dynamics. Here, we present a new approach to efficiently obtain AIMD trajectories in agreement with large, triple-ζ, polarized valence basis functions, at much reduced computational cost. For example, it follows from our studies that AIMD trajectories can indeed be constructed in agreement with basis sets such as 6-311++G(2df,2pd) with computational effort commensurate with those from much smaller basis sets such as 6-31+G(d), for polypeptide systems with 100+ atoms. The method is based on molecular fragmentation and allows a range-specified repartitioning of intramolecular (and potentially intermolecular) interactions where noncovalent interactions are selectively assembled using a piece-wise reconstruction based on a set-theoretic inclusion-exclusion principle generalization of ONIOM. Through a simplex decomposition of molecular systems the approach efficiently provides the necessary many-body interactions to faithfully represent noncovalent interactions at the large basis limit. Conformational stabilization energies are provided at close to the complete-basis limit at much reduced cost, and similarly AIMD trajectories (both Born-Oppenheimer and Car-Parrinello-type) are obtained in agreement with very large basis set sizes, in an extremely efficient and accurate manner. The method is demonstrated through simulations on polypeptide fragments of a variety of sizes.

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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: J Chem Theory Comput Ano de publicação: 2018 Tipo de documento: Artigo País de afiliação: Estados Unidos