The ability of simple potential functions to describe the properties of liquid water at a range of thermodynamic state points has been explored. These simple potential function models represent a water molecule by a set of sites, either rigid or flexible relative to each other, that interact with a simple, generally classical, Hamiltonian, which has parameters that are empirically determined. Calculations on several models that include intramolecular flexibility, electronic polarization or quantum mechanical effects have been performed. The consequences of altering these parameters have been systematically examined to determine factors of importance in reproducing properties of pure liquid water. It is found that simple four-site models that incorporate classical intramolecular flexibility or electronic polarization do not improve the description of the density anomaly of liquid water. Quantum statistical mechanical path integral calculations on the classical rigid nonpolarizable TIP5P model [J. Chem. Phys. 112, 8910 (2000)] and the classical flexible nonpolarizable TIP4F model indicate that although quantum mechanical effects destructure the rigid model, they improve the radial distribution and energy distribution properties of the flexible model. In addition, although quantum effects make the density behavior of the rigid model worse, they improve the density behavior of the flexible model. Path integral calculations have also been performed on quantum D2O TIP5P water; this leads to a temperature of maximum density that is higher and to a more structured liquid than results from calculations on quantum H2O TIP5P water. A similar effect is seen with calculations on a five-site rigid model, TIP5P(PIMC), which was parameterized using path integral rather than classical Monte Carlo calculations.
A computer program called CAMEO has been developed for the mechanistic discussion of nucleophilic reactions.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydration and energetics for tert-butyl chloride ion pairs in aqueous solutionWilliam L. Jorgensen, J. Kathleen Buckner, Shawn E. Huston, and Peter J. RosskyCite this: J. Am. Chem. Soc. 1987, 109, 7, 1891–1899Publication Date (Print):April 1, 1987Publication History Published online1 May 2002Published inissue 1 April 1987https://pubs.acs.org/doi/10.1021/ja00241a001https://doi.org/10.1021/ja00241a001research-articleACS PublicationsRequest reuse permissionsArticle Views457Altmetric-Citations98LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTComputer-assisted evaluation of oxidation reactionsGenevieve D. Paderes and William L. JorgensenCite this: J. Org. Chem. 1989, 54, 9, 2058–2085Publication Date (Print):April 28, 1989Publication History Published online1 May 2002Published inissue 28 April 1989https://pubs.acs.org/doi/10.1021/jo00270a014https://doi.org/10.1021/jo00270a014research-articleACS PublicationsRequest reuse permissionsArticle Views96Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTUse of statistical perturbation theory for computing solvent effects on molecular conformation: butane in waterWilliam L. Jorgensen and J. Kathleen. BucknerCite this: J. Phys. Chem. 1987, 91, 24, 6083–6085Publication Date (Print):November 1, 1987Publication History Published online1 May 2002Published inissue 1 November 1987https://pubs.acs.org/doi/10.1021/j100308a003https://doi.org/10.1021/j100308a003research-articleACS PublicationsRequest reuse permissionsArticle Views283Altmetric-Citations77LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts
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ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSimple prediction of substituent sensitivity (.rho.+) for carbocationsWilliam L. JorgensenCite this: J. Am. Chem. Soc. 1977, 99, 11, 3840–3842Publication Date (Print):May 1, 1977Publication History Published online1 May 2002Published inissue 1 May 1977https://pubs.acs.org/doi/10.1021/ja00453a055https://doi.org/10.1021/ja00453a055research-articleACS PublicationsRequest reuse permissionsArticle Views76Altmetric-Citations10LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
Free energies of solvation in liquid benzene and hexafluorobenzene have been computed for 42 uncharged solutes. Monte Carlo statistical mechanics was used with the free-energy perturbation theory and the OPLS-AA force field. The results address the transferability of the potential functions developed for pure liquids to mixed systems and the potential importance of explicit polarization for neutral organic molecules in aromatic solvents. Although the free-energy results cover an 11 kcal/mol range, the average error in comparison with experimental data points is only 0.4 kcal/mol. There is no systematic pattern to the discrepancies, so the need to add explicit treatment of solute-solvent polarization effects is not supported. This contrasts the situation with cationic solutes as reflected in cation-π interactions. Results for free energies of hydration are also provided for the 42 solutes in TIP4P water and give an average error of 0.49 kcal/mol. Implications for modeling biomolecular systems with standard force fields are considered. It is also interesting to note the overall similar values for free energies of solvation in benzene and hexafluorobenzene despite the reversal of polarity for the aromatic rings; the most significant exception is the more favorable solvation of perfluoroalkanes in the perfluoro solvent. Alternative accommodations of solutes in the two solvents are illustrated.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAn Extended Linear Response Method for Determining Free Energies of HydrationHeather A. Carlson and William L. JorgensenCite this: J. Phys. Chem. 1995, 99, 26, 10667–10673Publication Date (Print):June 1, 1995Publication History Published online1 May 2002Published inissue 1 June 1995https://pubs.acs.org/doi/10.1021/j100026a034https://doi.org/10.1021/j100026a034research-articleACS PublicationsRequest reuse permissionsArticle Views629Altmetric-Citations225LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStructure and properties of liquid ammoniaWilliam L. Jorgensen and Mustafa IbrahimCite this: J. Am. Chem. Soc. 1980, 102, 10, 3309–3315Publication Date (Print):May 1, 1980Publication History Published online1 May 2002Published inissue 1 May 1980https://pubs.acs.org/doi/10.1021/ja00530a001https://doi.org/10.1021/ja00530a001research-articleACS PublicationsRequest reuse permissionsArticle Views812Altmetric-Citations82LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
The inclusion of electronic polarization within Monte Carlo calculations of simple models of molecular liquids is hampered, relative to its inclusion within molecular dynamics calculations, by the need to fully determine the variables that specify the electronic configuration every time each molecule is moved, i.e., N times per cycle, rather than once per cycle. Classical statistical mechanical Monte Carlo calculations on two models of liquid water have been performed. For each of the models, electronic degrees of freedom are modeled by polarizable sites; thus it is the components of the induced dipole vector that must be determined at each step. Commonly used approximation methods have been characterized and found to be inadequate. Efficient procedures have been devised to estimate the dipole vector and have been tested on reproducing electronic, thermodynamic, and structural properties of the two polarizable water models. The most promising procedure, considering both computational time saved and accuracy at reproducing pure liquid properties, involves approximating the induced dipoles at each step by an initial perturbative modification of the dipoles from the previous step, followed by an iteration of the induced dipoles on only the moved molecule. With this procedure, the CPU time is dramatically reduced, and the thermodynamic and structural properties are estimated correctly to within a few percent. They are reproduced more rapidly and with greater accuracy than in calculations in which the dipole vector is estimated by a single iterative cycle starting with the dipoles from the previous Monte Carlo step.
