Understanding the Phase Diagram of Self-Assembled Monolayers of Alkanethiolates on Gold
Artikel i vetenskaplig tidskrift, 2016

Alkanethiolate monolayers on gold are important both for applications in nanoscience as well as fundamental studies of adsorption and self-assembly at metal surfaces. While considerable experimental effort has been put into understanding the phase diagram of these systems, theoretical work based on density functional theory (DFT) has long been hampered by the inability of conventional exchange-correlation functionals to describe dispersive interactions. In this work, we combine dispersion-corrected DFT calculations using the new vdW-DF-CX functional with the ab initio thermodynamics method to study the stability of dense standing-up and low-coverage lying-down phases on Au(111). We demonstrate that the lying-down phase has a thermodynamic region of stability starting from thiolates with alkyl chains consisting of n ? 3 methylene units. This phase emerges as a consequence of a competition between dispersive chain-chain and chain-substrate interactions, where the strength of the latter varies more strongly with n. A phase diagram is derived under ultrahigh-vacuum conditions, detailing the phase transition temperatures of the system as a function of the chain length. The present work illustrates that accurate ab initio modeling of dispersive interactions is both feasible and essential for describing self-assembled monolayers.


Joakim Löfgren

Chalmers, Fysik, Material- och ytteori

Henrik Grönbeck

Chalmers, Fysik, Kemisk fysik

Kasper Moth-Poulsen

Chalmers, Kemi och kemiteknik, Tillämpad kemi

Paul Erhart

Chalmers, Fysik, Material- och ytteori

Journal of Physical Chemistry C

1932-7447 (ISSN) 1932-7455 (eISSN)

Vol. 120 22 12059-12067

Single Molecule Nano Electronics (SIMONE)

Europeiska kommissionen (EU) (EC/FP7/337221), 2014-02-01 -- 2019-01-31.


Nanovetenskap och nanoteknik




Annan fysik


C3SE (Chalmers Centre for Computational Science and Engineering)



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