A priori calculations of the free energy of formation from solution of polymorphic self-Assembled monolayers

Jeffrey R. Reimers, Dwi Panduwinata, Johan Visser, Chunguang Tang, Lars Goerigk, Michael J. Ford, Maxine Sintic, Tze-Jing Sum, Michiel J.J. Coenen, Bas L.M. Hendriksen, Johannes A.A.W. Elemans, Noel S. Hush, Maxwell J. Crossley

Research output: Contribution to journalArticleAcademicpeer-review


Modern quantum chemical electronic structure methods typically applied to localized chemical bonding are developed to predict atomic structures and free energies for meso-tetraalkylporphyrin self-assembled monolayer (SAM) polymorph formation from organic solution on highly ordered pyrolytic graphite surfaces. Large polymorphdependent dispersion-induced substrate−molecule interactions (e.g., −100 kcal mol−1 to −150 kcal mol−1 for tetratrisdecylporphyrin) are found to drive SAM formation, opposed nearly completely by large polymorph-dependent dispersion-induced solvent interactions (70–110 kcal mol−1) and entropy effects (25–40 kcal mol−1 at 298 K) favoring dissolution. Dielectric continuum models of the solvent are used, facilitating consideration of many possible SAM polymorphs, along with quantum mechanical/molecular mechanical and dispersion-corrected density functional theory calculations. These predict and interpret newly measured and existing high-resolution scanning tunnelling microscopy images of SAM structure, rationalizing polymorph formation conditions. A wide range of molecular condensed matter properties at room temperature now appear suitable for prediction and analysis using electronic structure calculations.
Original languageEnglish
Pages (from-to)E6101 - E6110
Number of pages10
JournalProceedings of the National Academy of Sciences
Issue number45
Publication statusPublished - 28 Oct 2015
Externally publishedYes


  • self-assembled monolayers
  • density functional theory
  • dispersion
  • free energy
  • polymorphism


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