000013512 001__ 13512
000013512 005__ 20251007025657.0
000013512 02470 $$ahttps://doi.org/10.1021/acs.jctc.1c00609$$2doi
000013512 037__ $$aTEXTUAL
000013512 037__ $$bArticle
000013512 041__ $$aeng
000013512 245__ $$aUsing Constrained Density Functional Theory to Track Proton Transfers and to Sample Their Associated Free Energy Surface
000013512 269__ $$a2021-09-01
000013512 336__ $$aArticle
000013512 520__ $$aAb initio molecular dynamics (AIMD) and quantum mechanics/molecular mechanics (QM/MM) methods are powerful tools for studying proton solvation, transfer, and transport processes in various environments. However, due to the high computational cost of such methods, achieving sufficient sampling of rare events involving excess proton motion—especially when Grotthuss proton shuttling is involved—usually requires enhanced free energy sampling methods to obtain informative results. Moreover, an appropriate collective variable (CV) that describes the effective position of the net positive charge defect associated with an excess proton is essential both for tracking the trajectory of the defect and for the free energy sampling of the processes associated with the resulting proton transfer and transport. In this work, such a CV is derived from first principles using constrained density functional theory (CDFT). This CV is applicable to a broad array of proton transport and transfer processes as studied via AIMD and QM/MM simulations.
000013512 536__ $$oNational Institute of General Medical Sciences$$cR01 GM053148
000013512 536__ $$oU.S. Department of Energy$$cDE-SC0018648
000013512 540__ $$a<p>© 2021 The Authors.</p> <p>This publication is licensed under <a href="https://creativecommons.org/licenses/by/4.0/">CC-BY 4.0</a>.</p>
000013512 542__ $$fCC BY
000013512 690__ $$aPhysical Sciences Division
000013512 691__ $$aChemistry
000013512 692__ $$aChicago Center for Theoretical Chemistry
000013512 692__ $$aInstitute for Biophysical Dynamics
000013512 692__ $$aJames Franck Institute
000013512 7001_ $$aLi, Chenghan$$uUniversity of Chicago
000013512 7001_ $$1https://orcid.org/0000-0002-3267-6748$$2ORCID$$aVoth, Gregory A.$$uUniversity of Chicago
000013512 773__ $$tJournal of Chemical Theory and Computation
000013512 8564_ $$yArticle$$9df40273f-9981-479b-8f2a-41539a94182f$$s1466689$$uhttps://knowledge.uchicago.edu/record/13512/files/li-voth-2021-using-constrained-density-functional-theory-to-track-proton-transfers-and-to-sample-their-associated-free.pdf$$ePublic
000013512 8564_ $$ySupporting information$$9fa324908-f121-4e45-8392-cebd08b9bcab$$s234246$$uhttps://knowledge.uchicago.edu/record/13512/files/5598592.zip$$ePublic
000013512 908__ $$aI agree
000013512 909CO $$ooai:uchicago.tind.io:13512$$pGLOBAL_SET
000013512 983__ $$aArticle