Journal article

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

Jeffrey R Reimers, Dwi Panduwinata, Johan Visser, Yiing Chin, Chunguang Tang, Lars Goerigk, Michael J Ford, Maxine Sintic, Tze-Jing Sum, Michiel JJ Coenen, Bas LM Hendriksen, Johannes AAW Elemans, Noel S Hush, Maxwell J Crossley

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | NATL ACAD SCIENCES | Published : 2015

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 con..

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University of Melbourne Researchers

Grants

Awarded by Australian Research Council


Awarded by Council for the Chemical Sciences of the Netherlands Organization for Scientific Research


Awarded by European Research Council (ERC)


Awarded by Ministry of Education, Culture and Science


Funding Acknowledgements

We thank the Australian Research Council for funding this research (Grants LP0455238, DP12010259, and DE140100550) and National Computational Infrastructure and INTERSECT for provision of computing resources. J.A.A.W.E. thanks the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research for a Vidi Grant (700.58.423), and the European Research Council (ERC) for an ERC Starting Grant (NANOCAT-259064), and the Ministry of Education, Culture and Science (Gravity Program 024.001.035).