DC Field | Value | Language |
---|---|---|
dc.contributor.author | Kim, Yong-Hyun | ko |
dc.contributor.author | Kim, Kwiseon | ko |
dc.contributor.author | Zhang, S. B. | ko |
dc.date.accessioned | 2013-03-12T08:07:14Z | - |
dc.date.available | 2013-03-12T08:07:14Z | - |
dc.date.created | 2012-06-11 | - |
dc.date.created | 2012-06-11 | - |
dc.date.issued | 2012-04 | - |
dc.identifier.citation | JOURNAL OF CHEMICAL PHYSICS, v.136, no.13 | - |
dc.identifier.issn | 0021-9606 | - |
dc.identifier.uri | http://hdl.handle.net/10203/101735 | - |
dc.description.abstract | Despite 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.language | English | - |
dc.publisher | AMER INST PHYSICS | - |
dc.subject | DENSITY-FUNCTIONAL THEORY | - |
dc.subject | WATER | - |
dc.subject | DYNAMICS | - |
dc.subject | PK(A) | - |
dc.subject | GAAS | - |
dc.subject | SEMICONDUCTORS | - |
dc.subject | HYDROLYSIS | - |
dc.subject | POTENTIALS | - |
dc.subject | ENERGETICS | - |
dc.subject | SOLVATION | - |
dc.title | First-principles calculation of thermodynamic stability of acids and bases under pH environment: A microscopic pH theory | - |
dc.type | Article | - |
dc.identifier.wosid | 000302596500014 | - |
dc.identifier.scopusid | 2-s2.0-84861666471 | - |
dc.type.rims | ART | - |
dc.citation.volume | 136 | - |
dc.citation.issue | 13 | - |
dc.citation.publicationname | JOURNAL OF CHEMICAL PHYSICS | - |
dc.identifier.doi | 10.1063/1.3700442 | - |
dc.contributor.localauthor | Kim, Yong-Hyun | - |
dc.contributor.nonIdAuthor | Kim, Kwiseon | - |
dc.contributor.nonIdAuthor | Zhang, S. B. | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | DENSITY-FUNCTIONAL THEORY | - |
dc.subject.keywordPlus | WATER | - |
dc.subject.keywordPlus | DYNAMICS | - |
dc.subject.keywordPlus | PK(A) | - |
dc.subject.keywordPlus | GAAS | - |
dc.subject.keywordPlus | SEMICONDUCTORS | - |
dc.subject.keywordPlus | HYDROLYSIS | - |
dc.subject.keywordPlus | POTENTIALS | - |
dc.subject.keywordPlus | ENERGETICS | - |
dc.subject.keywordPlus | SOLVATION | - |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.