Statistical mechanical models for dissociative adsorption of O2 on metal(100) surfaces with blocking, steering, and funneling

نویسندگان

  • Da-Jiang Liu
  • James W. Evans
چکیده

We develop statistical mechanical models amenable to analytic treatment for the dissociative adsorption of O2 at hollow sites on fcc(100) metal surfaces. The models incorporate exclusion of nearest-neighbor pairs of adsorbed O. However, corresponding simple site-blocking models, where adsorption requires a large ensemble of available sites, exhibit an anomalously fast initial decrease in sticking. Thus, in addition to blocking, our models also incorporate more facile adsorption via orientational steering and funneling dynamics (features supported by ab initio Molecular Dynamics studies). Behavior for equilibrated adlayers is distinct from those with finite adspecies mobility. We focus on the low-temperature limited-mobility regime where analysis of the associated master equations readily produces exact results for both shortand long-time behavior. Kinetic Monte Carlo simulation is also utilized to provide a more complete picture of behavior. These models capture both the initial decrease and the saturation of the experimentally observed sticking versus coverage, as well as features of non-equilibrium adlayer ordering as assessed by surface-sensitive diffraction.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Statistical mechanical models for dissociative adsorption of O₂ on metal(100) surfaces with blocking, steering, and funneling.

We develop statistical mechanical models amenable to analytic treatment for the dissociative adsorption of O2 at hollow sites on fcc(100) metal surfaces. The models incorporate exclusion of nearest-neighbor pairs of adsorbed O. However, corresponding simple site-blocking models, where adsorption requires a large ensemble of available sites, exhibit an anomalously fast initial decrease in sticki...

متن کامل

Dissociative adsorption of O2 on unreconstructed metal (100) surfaces: Pathways, energetics, and sticking kinetics

An accurate description of oxygen dissociation pathways and kinetics for various local adlayer environments is key for an understanding not just of the coverage dependence of oxygen sticking, but also of reactive steady states in oxidation reactions. Density functional theory analysis for M(100) surfaces with M=Pd, Rh, and Ni, where O prefers the fourfold hollow adsorption site, does not suppor...

متن کامل

Non-Dissociative Gas Adsorption with Different Chemisorption Geometries on Nanoporous Surfaces

Isotherm equation is one of the important scientific bases for adsorbent selection. There are different isotherms that do not account for an adsorbate, different chemisorption geometries on the nanoporous surface. It is interesting to introduce a general isotherm, which considers different chemisorption geometries of an adsorbate on nanoporous surfaces. In this study, an isotherm for non-dissoci...

متن کامل

Steering and ro-vibrational effects in the dissociative adsorption and associative desorption of H2/Pd(100)

The interaction of hydrogen with many transition metal surfaces is characterized by a coexistence of activated with non-activated paths to adsorption with a broad distribution of barrier heights. By performing six-dimensional quantum dynamical calculations using a potential energy surface derived from ab initio calculations for the system H2/Pd(100) we show that these features of the potential ...

متن کامل

ar X iv : m tr l - th / 9 60 90 09 v 1 2 5 Se p 19 96 Steering and isotope effects in the dissociative adsorption of H / Pd ( 100 )

The interaction of hydrogen with many transition metal surfaces is characterized by a coexistence of activated with non-activated paths to adsorption with a broad distribution of barrier heights. By performing six-dimensional quantum dynamical and classical molecular dynamics calculations using the same potential energy surface derived from ab initio calculations for the system H2/Pd(100) we sh...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 2017