Effects of van der Waals Interactions in the Adsorption of Isooctane and Ethanol on Fe(100) Surfaces

Bedolla, Pedro O.; Feldbauer, Gregor; Wolloch, Michael; Eder, Stefan J.; Dörr, Nicole; Mohn, P.; Redinger, Josef; Vernes, A.

doi:10.1021/jp503829c

Cited by 63 publications

(58 citation statements)

References 78 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…vdW-DFs have been applied to a wide range of materials (e.g., see Refs. [75][76][77][78][79][80][81][82][83] and have proven to be of good accuracy. Although vdW interactions should not play a major role in the investigated systems, the calculations are included for comparison and clarification.…”

Section: A Density Functional Theory Calculationsmentioning

confidence: 99%

Adhesion and material transfer between contacting Al and TiN surfaces from first principles

et al. 2015

View full text Add to dashboard Cite

A series of density functional theory (DFT) simulations was performed to investigate the approach, contact, and subsequent separation of two atomically flat surfaces consisting of different materials. Aluminum (Al) and titanium nitride (TiN) slabs were chosen as a model system representing a metal-ceramic interface and the interaction between soft and hard materials. The approach and separation were simulated by moving one slab in discrete steps normal to the surfaces allowing for electronic and atomic relaxations after each step. Various configurations were analyzed by considering (001), (011), and (111) surfaces as well as several lateral arrangements of these surfaces at the interface. Several tests were conducted on the computational setup, for example, by changing the system size or using different approximations for the exchange correlation functional. The performed simulations revealed the influences of these aspects on adhesion, equilibrium distance, and material transfer. These interfacial properties depend sensitively on the chosen configuration due to distinct bond situations. Material transfer, in particular, was observed if the absolute value of the adhesion energy for a given configuration is larger than the energy cost to remove surface layers. This result was found to be independent of the employed exchange correlation functional. Furthermore, it was shown that a simple comparison of the surface energies of the slabs is not sufficient to predict the occurrence of material transfer.

show abstract

Section: A Density Functional Theory Calculationsmentioning

confidence: 99%

Adhesion and material transfer between contacting Al and TiN surfaces from first principles

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Surface chemistry is distinct from bulk chemistry due to the effect of unbalanced van der Waals forces (e.g., [323][324][325]) and electric moments of solution electrolytes. As discussed in the cited references, the surface energy effects are comparable to the molecular kinetic energy which is central to reaction kinetics.…”

Section: Brief Theoretical Overviewmentioning

confidence: 99%

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

Semeniuk

Dastoor

2020

Atmosphere

View full text Add to dashboard Cite

A useful aerosol model must be able to adequately resolve the chemical complexity and phase state of the wide particle size range arising from the many different secondary aerosol growth processes to assess their environmental and health impacts. Over the past two decades, significant advances in understanding of gas-aerosol partitioning have occurred, particularly with respect to the role of organic compounds, yet aerosol representations have changed little in air quality and climate models since the late 1990s and early 2000s. The gas-aerosol partitioning models which are still commonly used in air quality models are separate inorganics-only thermodynamics and secondary organic aerosol (SOA) formation based on absorptive partitioning theory with an assumption of well-mixed liquid-like particles that continuously maintain equilibrium with the gas phase. These widely used approaches in air quality models for secondary aerosol composition and growth based on separated inorganic and organic processes are inadequate. This review summarizes some of the important developments during the past two decades in understanding of gas aerosol mass transfer processes. Substantial increases in computer performance in the last decade justify increasing the process detail in aerosol models. Organics play a central role during post-nucleation growth into the accumulation mode and change the hygroscopic properties of sulfate aerosol. At present, combined inorganic-organic aerosol thermodynamics models are too computationally expensive to be used online in 3-D simulations without high levels of aggregation of organics into a small number of functional surrogates. However, there has been progress in simplified modeling of liquid-liquid phase separation (LLPS) and distinct chemical regimes within organic-rich and inorganic-rich phases. Additional limitations of commonly used thermodynamics models are related to lack of surface tension data for various aerosol compositions in the small size limit, and lack of a comprehensive representation of surface interaction terms such as disjoining pressure in the Gibbs free energy which become significant in the small size limit and which affect both chemical composition and particle growth. As a result, there are significant errors in modeling of hygroscopic growth and phase transitions for particles in the nucleation and Aitken modes. There is also increasing evidence of reduced bulk diffusivity in viscous organic particles and, therefore, traditional secondary organic aerosol models, which are typically based on the assumption of instantaneous equilibrium gas-particle partitioning and neglect the kinetic effects, are no longer tenable.

show abstract

“…Weak van der Waals interactions, typically ignored in the presence of covalent bonds, take center stage in determining the favorable adsorption sites on the catalyst surfaces. In addition to catalyst design, noncovalent interactions between organic molecules and planar single crystal metal surfaces have also been recently studied in the context of self-assembled monolayer (SAM) systems and identified as the principal factor in determining the assembly patterns [30][31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111)

et al. 2016

View full text Add to dashboard Cite

Gold-based heterogeneous catalysts have attracted significant attention due to their selective partial oxidation capabilities, providing promising alternatives for the traditional industrial homogeneous catalysts. In the current study, the energetics of adsorption/desorption of alcohols (CH3OH/methanol, CH3CH2OH/ethanol, CH3CH2CH2OH/n-propanol) and esters (HCOOCH3/methyl formate, CH3COOCH3/methyl acetate, and CH3COOCH2CH3/ethyl acetate) on a planar Au(111) surface was investigated in conjunction with oxidative coupling reactions by means of temperature programmed desorption (TPD) and dispersion-corrected density functional theory (DFT) calculations. The results reveal a complex interplay between inter-molecular and surface-molecule interactions, both mediated by weak van der Waals forces, which dictates their relative stability on the gold surface. Both experimental and theoretical adsorption/desorption energies of the investigated esters are lower than those of the alcohols from which they originate through oxidative coupling reactions. This result can be interpreted as an important indication in favor of the selectivity of Au surfaces in alcohol oxidative coupling/partial oxidation reactions, allowing facile removal of partial oxidation products immediately after their generation preventing their complete oxidation to higher oxygenates

show abstract

Effects of van der Waals Interactions in the Adsorption of Isooctane and Ethanol on Fe(100) Surfaces

Cited by 63 publications

References 78 publications

Adhesion and material transfer between contacting Al and TiN surfaces from first principles

Adhesion and material transfer between contacting Al and TiN surfaces from first principles

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

Comparative Analysis of Reactant and Product Adsorption Energies in the Selective Oxidative Coupling of Alcohols to Esters on Au(111)

Contact Info

Product

Resources

About