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

Reimers, JR; Panduwinata, D; Visser, J; Chin, Y; Tang, C; Goerigk, L; Ford, MJ; Sintic, M; Sum, TJ; Coenen, MJJ; Hendriksen, BLM; Elemans, JAAW; Hush, NS; Crossley, MJ

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

Reimers, JR

Panduwinata, D Visser, J Chin, Y Tang, C Goerigk, L Ford, MJ

Sintic, M Sum, TJ Coenen, MJJ Hendriksen, BLM Elemans, JAAW Hush, NS Crossley, MJ

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Publication Type:: Journal Article
Citation:: Proceedings of the National Academy of Sciences of the United States of America, 2015, 112 (45), pp. E6101 - E6110
Issue Date:: 2015-11-10

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Field	Value	Language
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Panduwinata, D	en_US
dc.contributor.author	Visser, J	en_US
dc.contributor.author	Chin, Y	en_US
dc.contributor.author	Tang, C	en_US
dc.contributor.author	Goerigk, L	en_US
dc.contributor.author	Ford, MJ https://orcid.org/0000-0002-8595-5900	en_US
dc.contributor.author	Sintic, M	en_US
dc.contributor.author	Sum, TJ	en_US
dc.contributor.author	Coenen, MJJ	en_US
dc.contributor.author	Hendriksen, BLM	en_US
dc.contributor.author	Elemans, JAAW	en_US
dc.contributor.author	Hush, NS	en_US
dc.contributor.author	Crossley, MJ https://orcid.org/0000-0001-5157-7422	en_US
dc.date.available	2015-09-15	en_US
dc.date.issued	2015-11-10	en_US
dc.identifier.citation	Proceedings of the National Academy of Sciences of the United States of America, 2015, 112 (45), pp. E6101 - E6110	en_US
dc.identifier.issn	0027-8424	en_US
dc.identifier.uri	http://hdl.handle.net/10453/42188
dc.description.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 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.	en_US
dc.relation.ispartof	Proceedings of the National Academy of Sciences of the United States of America	en_US
dc.relation.isbasedon	10.1073/pnas.1516984112	en_US
dc.title	A priori calculations of the free energy of formation from solution of polymorphic self-Assembled monolayers	en_US
dc.type	Journal Article
utslib.citation.volume	45	en_US
utslib.citation.volume	112	en_US
utslib.for	0204 Condensed Matter Physics	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/DVC (Research)
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	closed_access
pubs.issue	45	en_US
pubs.publication-status	Published	en_US
pubs.volume	112	en_US

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 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.

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http://hdl.handle.net/10453/42188