Thermodynamics of Alkanethiol Self-Assembled Monolayer Assembly on Pd Surfaces

Langmuir : the ACS Journal of Surfaces and Colloids
Gaurav KumarMichael J Janik

Abstract

We investigate the structure and binding energy of alkanethiolate self-assembled monolayers (SAMs) on Pd (111), Pd (100), and Pd (110) facets at different coverages. Dispersion-corrected density functional theory calculations are used to correlate the binding energy of alkanethiolates with alkyl chain length and coverage. The equilibrium coverage of thiolate layers strongly prefers 1/3 monolayer (ML) on the Pd (111) surface. The coverage of thiolates varies with chemical potential on Pd (100) and Pd (110), increasing from 1/3 to 1/2 ML on (100) and from 1/4 to 1/2 ML on (110) as the thiol chemical potential is increased. Higher coverages are driven by attractive dispersion interactions between the extended alkyl chains, such that transitions to higher coverages occur at lower thiol chemical potentials for longer chain thiolates. Stronger adsorption to the Pd (100) surface causes the equilibrium Wulff construction of Pd particles to take on a cubic shape upon saturation with thiols. The binding of H, O, and CO adsorbates is weakened as the thiolate coverage is increased, with saturation coverages causing unfavorable binding of O and CO on Pd (100) and weakened binding on other facets. Temperature-dependent CO diffuse reflectance...Continue Reading

References

Oct 15, 1996·Physical Review. B, Condensed Matter·G Kresse, J Furthmüller
Nov 15, 1996·Physical Review. B, Condensed Matter·I H CampbellJ P Ferraris
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jun 20, 1996·Chemical Reviews·Abraham Ulman
Feb 21, 2002·Journal of the American Chemical Society·J Christopher LoveGeorge M Whitesides
Feb 27, 2003·Journal of the American Chemical Society·J Christopher LoveRalph G Nuzzo
Nov 13, 2003·Chemical Reviews·Stephan KrämerChristopher B Gorman
Jul 9, 2004·Journal of the American Chemical Society·Bhanu P S ChauhanTariq Bandoo
Apr 14, 2005·Chemical Reviews·J Christopher LoveGeorge M Whitesides
Apr 14, 2005·Chemical Reviews·Byron D GatesGeorge M Whitesides
Nov 1, 2006·Langmuir : the ACS Journal of Surfaces and Colloids·Francisco J Ibañez, Francis P Zamborini
Sep 9, 2008·Langmuir : the ACS Journal of Surfaces and Colloids·Chiranjib Majumder
Oct 29, 2008·Physical Chemistry Chemical Physics : PCCP·Laurent PiccoloGilles Berhault
Aug 25, 2009·Langmuir : the ACS Journal of Surfaces and Colloids·Laxman KankateArmin Gölzhäuser
Aug 24, 2010·Langmuir : the ACS Journal of Surfaces and Colloids·Pilar CarroRoberto C Salvarezza
Sep 14, 2010·Nature Materials·Stephen T MarshallJ William Medlin
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Mar 27, 2012·Accounts of Chemical Research·Evangelina PensaRoberto C Salvarezza
May 10, 2012·Journal of the American Chemical Society·John E MatthiesenKenneth J Klabunde
Sep 13, 2012·Advanced Materials·Tomoya TaguchiKazushi Miki
Aug 2, 2013·The Journal of Chemical Physics·Thomas P SenftleAdri C T van Duin
Sep 13, 2013·Nature Communications·Simon H PangJ Will Medlin
Mar 19, 2014·Accounts of Chemical Research·Carolyn A SchoenbaumJ Will Medlin
Sep 14, 2016·Scientific Data·Richard TranShyue Ping Ong

❮ Previous
Next ❯

Citations

Jan 16, 2020·Physical Chemistry Chemical Physics : PCCP·Benjamin SchweitzerDiego A Gómez-Gualdrón
Jun 15, 2021·Chemical Science·Thierry K SlotGadi Rothenberg
May 21, 2020·ACS Applied Materials & Interfaces·Michael SiemerKatharina Al-Shamery
Sep 10, 2021·Nano Convergence·Christina BoukouvalaEmilie Ringe

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.