Robust and Efficient Constrained DFT Molecular Dynamics Approach for Biochemical Modeling.

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Constrained density functional theory (cDFT) is crucial for studying electron dynamics in physical-chemical processes.
• Accurate computational methods are needed to model complex electron transfer (ET) reactions and quantum decoherence.

Purpose of the Study:

• To present recent advancements in the parallelized implementation of cDFT within the deMon2k program.
• To improve the computational efficiency of cDFT for calculating electronic coupling and quantum decoherence.

Main Methods:

• Implementation of cDFT using linear combinations of Hermite Gaussian functions for atomic densities.
• Improved computation of cDFT integration weights via Hirshfeld and Voronoi deformation density approaches.
• Utilized cDFT and hybrid cDFT/molecular mechanics molecular dynamics simulations for sampling.

Main Results:

• Demonstrated enhanced efficiency of the cDFT method on electron transfer calculations through glycine polypeptides.
• Reported the first estimations of quantum decoherence times derived from cDFT-based simulations for ET reactions.

Conclusions:

• The improved cDFT implementation in deMon2k offers a more efficient approach for studying electron dynamics.
• This work provides new insights into electron transfer mechanisms and quantum decoherence phenomena.