title: A priori calculations of the free energy of formation from solution of polymorphic self-assembled monolayers.
abstract: 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 polymorph-dependent 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.
authors.affiliation: International Centre for Quantum and Molecular Structure, College of Sciences, Shanghai University, Shanghai 200444, China; School of Mathematical and Physical Sciences, The University of Technology Sydney, Sydney, NSW 2007, Australia; reimers@shu.edu.cn noel.hush@sydney.edu.au jeffrey.reimers@uts.edu.au maxwell.crossley@sydney.edu.au.
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Reimers
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia;
authors.forename: Dwi
authors.initials: D
authors.lastname: Panduwinata
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia;
authors.forename: Johan
authors.initials: J
authors.lastname: Visser
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia;
authors.forename: Yiing
authors.initials: Y
authors.lastname: Chin
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia;
authors.forename: Chunguang
authors.initials: C
authors.lastname: Tang
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia; School of Chemistry, The University of Melbourne, Melbourne, VIC 3010, Australia;
authors.forename: Lars
authors.initials: L
authors.lastname: Goerigk
authors.affiliation: School of Mathematical and Physical Sciences, The University of Technology Sydney, Sydney, NSW 2007, Australia;
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Ford
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia;
authors.forename: Maxine
authors.initials: M
authors.lastname: Sintic
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia;
authors.forename: Tze-Jing
authors.initials: TJ
authors.lastname: Sum
authors.affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, 6525 AJ Nijmegen, The Netherlands;
authors.forename: Michiel J J
authors.initials: MJ
authors.lastname: Coenen
authors.affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, 6525 AJ Nijmegen, The Netherlands;
authors.forename: Bas L M
authors.initials: BL
authors.lastname: Hendriksen
authors.affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, 6525 AJ Nijmegen, The Netherlands;
authors.forename: Johannes A A W
authors.initials: JA
authors.lastname: Elemans
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia; School of Biomolecular Science, The University of Sydney, Sydney, NSW 2006, Australia reimers@shu.edu.cn noel.hush@sydney.edu.au jeffrey.reimers@uts.edu.au maxwell.crossley@sydney.edu.au.
authors.forename: Noel S
authors.initials: NS
authors.lastname: Hush
authors.affiliation: School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia; reimers@shu.edu.cn noel.hush@sydney.edu.au jeffrey.reimers@uts.edu.au maxwell.crossley@sydney.edu.au.
authors.forename: Maxwell J
authors.initials: MJ
authors.lastname: Crossley
keywords: density functional theory; dispersion; free energy; polymorphism; self-assembled monolayers