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Density functional tight binding‐based free energy simulations in the DFTB+ program
Author(s) -
Mitchell Izaac,
Aradi Bálint,
Page Alister J.
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25583
Subject(s) - metadynamics , tight binding , maxima and minima , molecular dynamics , chemistry , chemical physics , proton , computational chemistry , electronic structure , physics , mathematical analysis , mathematics , quantum mechanics
The timescale problem—in which high barriers on the free energy surface trap molecular dynamics simulations in local energy wells—is a key limitation of current reactive MD simulations based on the density functional tight binding (DFTB) potential. Here, we report a new interface between the DFTB+ software package and the PLUMED library for performing DFTB‐based free energy calculations. We demonstrate the performance of this interface for 3 archetypal rare‐event chemical reactions, (i) intramolecular proton transfer in malonaldehyde, (ii) bowl inversion in corannulene, and (iii) oxygen diffusion on graphene. Using third‐order DFTB in conjunction with metadynamics (with/without multiple walkers) and well‐tempered metadynamics, we report here free energies of activation (Δ G ‡ ) of 13.1 ± 0.4, 48.2 ± 1.7, and 52.0 ± 6.2 kJ mol −1 , respectively, for these processes. In each case, our DFTB free energy barriers and local minima compare favorably with previous literature results, demonstrating the utility of the DFTB+ ‐ PLUMED interface. © 2018 Wiley Periodicals, Inc.