First-principles calculation of thermodynamic stability of acids and bases under pH environment: A microscopic pH theory

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dc.contributor.authorKim, Yong-Hyunko
dc.contributor.authorKim, Kwiseonko
dc.contributor.authorZhang, S. B.ko
dc.date.accessioned2013-03-12T08:07:14Z-
dc.date.available2013-03-12T08:07:14Z-
dc.date.created2012-06-11-
dc.date.created2012-06-11-
dc.date.issued2012-04-
dc.identifier.citationJOURNAL OF CHEMICAL PHYSICS, v.136, no.13-
dc.identifier.issn0021-9606-
dc.identifier.urihttp://hdl.handle.net/10203/101735-
dc.description.abstractDespite being one of the most important thermodynamic variables, pH has yet to be incorporated into first-principles thermodynamics to calculate stability of acidic and basic solutes in aqueous solutions. By treating the solutes as defects in homogeneous liquids, we formulate a first-principles approach to calculate their formation energies under proton chemical potential, or pH, based on explicit molecular dynamics. The method draws analogy to first-principle calculations of defect formation energies under electron chemical potential, or Fermi energy, in semiconductors. From this, we propose a simple pictorial representation of the general theory of acid-base chemistry. By performing first-principles molecular dynamics of liquid water models with solutes, we apply the formulation to calculate formation energies of various neutral and charged solutes such as H+, OH-, NH3, NH4+, HCOOH, and HCOO-in water. The deduced auto-dissociation constant of water and the difference in the pKa values of NH3 and HCOOH show good agreement with known experimental values. Our first-principles approach can be further extended and applied to other bio- and electro-chemical molecules such as amino acids and redox reaction couples that could exist in aqueous environments to understand their thermodynamic stability. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3700442]-
dc.languageEnglish-
dc.publisherAMER INST PHYSICS-
dc.subjectDENSITY-FUNCTIONAL THEORY-
dc.subjectWATER-
dc.subjectDYNAMICS-
dc.subjectPK(A)-
dc.subjectGAAS-
dc.subjectSEMICONDUCTORS-
dc.subjectHYDROLYSIS-
dc.subjectPOTENTIALS-
dc.subjectENERGETICS-
dc.subjectSOLVATION-
dc.titleFirst-principles calculation of thermodynamic stability of acids and bases under pH environment: A microscopic pH theory-
dc.typeArticle-
dc.identifier.wosid000302596500014-
dc.identifier.scopusid2-s2.0-84861666471-
dc.type.rimsART-
dc.citation.volume136-
dc.citation.issue13-
dc.citation.publicationnameJOURNAL OF CHEMICAL PHYSICS-
dc.identifier.doi10.1063/1.3700442-
dc.contributor.localauthorKim, Yong-Hyun-
dc.contributor.nonIdAuthorKim, Kwiseon-
dc.contributor.nonIdAuthorZhang, S. B.-
dc.type.journalArticleArticle-
dc.subject.keywordPlusDENSITY-FUNCTIONAL THEORY-
dc.subject.keywordPlusWATER-
dc.subject.keywordPlusDYNAMICS-
dc.subject.keywordPlusPK(A)-
dc.subject.keywordPlusGAAS-
dc.subject.keywordPlusSEMICONDUCTORS-
dc.subject.keywordPlusHYDROLYSIS-
dc.subject.keywordPlusPOTENTIALS-
dc.subject.keywordPlusENERGETICS-
dc.subject.keywordPlusSOLVATION-
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