Modeling fundamental properties of Metal-organic Species at Solvent and Non-solvent Mediated Interfaces
EMSL Project ID
48783
Abstract
The proposed research will focus on investigating interfacial processes and properties of metal-organic films in solvent and non-solvent mediated interfaces. The goal is to understand the kinetics and thermodynamics of chemical reactions occurring at the interfaces in the molecular level using computational modeling. We use porphyrins as model metal-organic systems of fundamental and technological importance. Adsorption and desorption properties of ligated and unligated metalloporphyrins on surfaces will be studied to aid the scanning tunneling microscopy (STM) experiments in vacuum and in solvent. Multiple adsorbates (porphyrins with various 3d transition metals), adsorbents (gold, graphite), ligands (differing sigma and pi donor strengths) and solvents (both implicit and explicit solvation) will be considered in our study. Simulations with ab-initio electronic structure methods and molecular dynamics will be used to study the role of substrate, adsorbate, solvent and their interactions in forming a monolayer/thin-film. Computations proposed here will also help in determining the kinetic and thermodynamic parameters which govern dynamic equilibrium at the solution-solid interface. Ability to qualitatively and quantitatively measure the kinetic and thermodynamic parameters of single molecules at the interface is critical to achieving the desirable goal of predicting the surface structures and their chemical and electronic properties. We will use EMSL’s state of the art Cascade supercomputer to perform our computations. The results from these computations will have immediate significance toward understanding interfacial processes and surface science. On a broader impact, these studies provide insight into kinetics and thermodynamics of single molecules at vacuum-solid, solid-solid and solution-solid interfaces. Thus, they bear applications toward developing and tuning fundamental processes occurring at interfaces in optical, electronic and sensing devices, catalysis and battery development.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2015-10-01
End Date
2017-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Adinehnia M ,Borders B ,Ruf M ,Chilukuri B ,Hipps K W,Mazur U 2016. "Comprehensive structure–Function Correlation of Photoactive Ionic ?-Conjugated Supermolecular Assemblies: an Experimental and Computational Study" Journal of Materials Chemistry C 4(43):10223-10239. 10.1039/C6TC03957J
Borders B., M. Adinehnia, B. Chilukuri, M. Ruf, K.W. Hipps, and U. Mazur. 2018. "Tuning the Optoelectronic Characteristics of Ionic Organic Crystalline Assemblies." Journal of Materials Chemistry C 6. doi:10.1039/c8tc00416a
Borders B., M. Adinehnia, B. Chilukuri, M. Ruf, K.W. Hipps, and U. Mazur. 2018. "Tuning the Optoelectronic Characteristics of Ionic Organic Crystalline Assemblies." Journal of Materials Chemistry C 6. doi:10.1039/c8tc00416a
Chilukuri B ,Mcdougald R N,Ghimire M ,Nesterov V ,Mazur U ,Omary M A,Hipps K W 2015. "Polymorphic, Porous, and Host–Guest Nanostructures Directed by Monolayer–Substrate Interactions: Epitaxial Self-Assembly Study of Cyclic Trinuclear Au(I) Complexes on HOPG at the Solution–Solid Interface" Journal of Physical Chemistry C 119(44):24844–24858. 10.1021/acs.jpcc.5b08171
Chilukuri B., U. Mazur, and K.W. Hipps. 2019. "Cooperativity and Coverage Dependent MolecularDesorption in Self-assembled Monolayers: Computational Case Study with Coronene on Au(111) and HOPG." Physical Chemistry Chemical Physics. PCCP 21. doi:10.1039/C9CP01774G
Jahanbekam A ,Chilukuri B ,Mazur U ,Hipps K W 2015. "Kinetically Trapped Two-Component Self-Assembled Adlayer" Journal of Physical Chemistry C 119(45):25364–25376. 10.1021/acs.jpcc.5b07120
Nandi G ,Chilukuri B ,Hipps K W,Mazur U 2016. "Surface Directed Reversible Imidazole Ligation to Nickel(II) Octaethylporphyrin at the Solution/Solid Interface: a Single Molecule Level Study" Physical Chemistry Chemical Physics. PCCP 18(30):20819-20829. 10.1039/C6CP04454A