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This would be of quantitative significance since for instance pKa values are affected by deuteration. Moreover, the absence of assumptions or impositions about reactive candidates or reaction paths allows extending this method to systems of increasing complexity which cannot be addressed with traditional methods. Examples of questions that can now be answered are tautomeric equilibria in biochemical processes and acid behavior in zeolites and on the surface of oxides exposed to water. MethodsAs discussed above we introduce two CVs, one related to the protonation state and another that locates the charge defects and measures their relative distance.

ResultsWe have applied our method to three aqueous solutions of acetic acid, ammonia, and bicarbonate as representations journal clinical pharmacology and therapeutics a weak acid, a weak base, and an infp personality character compound, respectively.

ConclusionsThe general applicability of this method to systems with different natures is an important step made in their understanding and description.

OpenUrlHo J, Coote ML (2009) A universal approach for continuum solvent pKa calculations: Are we there yet. OpenUrlSilva CO, da Silva EC, Nascimento MAC (2000) Ab initio calculations of absolute pKa values in aqueous solution II. Aliphatic alcohols, thiols, and halogenated carboxylic acids. OpenUrlRebollar-Zepeda AM, Galano A (2016) Quantum mechanical based approaches for predicting pKa values of carboxylic acids: Evaluating the performance of different strategies.

OpenUrlDavies JE, Doltsinis NL, Kirby AJ, Roussev CD, Sprik M (2002) Estimating pKa values for pentaoxyphosphoranes. OpenUrlCrossRefPubMedPark JM, Laio A, Iannuzzi M, Parrinello M (2006) Dissociation mechanism of acetic acid in water.

OpenUrlCrossRefPubMedTummanapelli AK, Vasudevan S (2014) Dissociation constants of journal clinical pharmacology and therapeutics acids from ab initio molecular dynamics using metadynamics: Influence of the inductive effect and hydrogen bonding on pKa values.

J Chem Phys 149:072320. OpenUrlLee J-G, et al. OpenUrlPubMedBernardi RC, Melo MCR, Schulten K (2015) Enhanced sampling techniques in molecular dynamics simulations of biological systems. OpenUrlCrossRefPubMedLaio A, Parrinello M (2002) Escaping free-energy minima. OpenUrlTorrie GM, Valleau JP (1977) Nonphysical sampling distributions in Monte Carlo free-energy estimation: Umbrella sampling. OpenUrlCrossRefPiccini G, McCarty JJ, Valsson O, Parrinello M (2017) Variational flooding journal clinical pharmacology and therapeutics of a SN2 reaction.

OpenUrlMendels D, Piccini G, Parrinello M (2018) Collective variables from local fluctuations. OpenUrlPiccini G, Polino D, Parrinello M (2017) Identifying slow molecular motions in complex chemical reactions. OpenUrlAgmon N (1995) The Grotthuss mechanism. OpenUrlCrossRefZundel G, Metzger H (1968) Energiebander der tunnelnden uberschu-protonen in flussigen sauren. OpenUrlCrossRefMarx D, Tuckerman ME, Hutter J, Parrinello M (1999) The nature of the hydrated excess proton in water.

OpenUrlIyengar SS, et al. Journal clinical pharmacology and therapeutics protonated 21-water cluster. OpenUrlBarducci A, Bussi G, Parrinello M (2008) Well-tempered metadynamics: A smoothly converging and tunable free-energy method. OpenUrlCrossRefVandevondele J, et journal clinical pharmacology and therapeutics. Phys Rev X 6:041005. OpenUrlCrossRefParrinello M, Desmopressin Acetate Rhinal Tube (DDAVP Rhinal Tube)- FDA A (1984) Study of an F center in molten KCl.

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