skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

Abstract

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Massachusetts, Amherst, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1344088
Grant/Contract Number:  
FG02-87ER13744
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Farjamnia, Azar, and Jackson, Bret. The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study. United States: N. p., 2017. Web. doi:10.1063/1.4976132.
Farjamnia, Azar, & Jackson, Bret. The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study. United States. https://doi.org/10.1063/1.4976132
Farjamnia, Azar, and Jackson, Bret. Tue . "The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study". United States. https://doi.org/10.1063/1.4976132. https://www.osti.gov/servlets/purl/1344088.
@article{osti_1344088,
title = {The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study},
author = {Farjamnia, Azar and Jackson, Bret},
abstractNote = {A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.},
doi = {10.1063/1.4976132},
url = {https://www.osti.gov/biblio/1344088}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 7,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Mechanistic Studies of Water–Gas-Shift Reaction on Transition Metals
journal, September 2011


The temperature dependence of methane dissociation on Ni(111) and Pt(111): Mixed quantum-classical studies of the lattice response
journal, April 2010


Generalized Gradient Approximation Made Simple
journal, October 1996


Catalysis Research of Relevance to Carbon Management:  Progress, Challenges, and Opportunities
journal, April 2001


Dissociative Chemisorption of Methane on Pt(110)-(1×2): Effects of Lattice Motion on Reactions at Step Edges
journal, May 2013


On the Analytical Mechanics of Chemical Reactions. Quantum Mechanics of Linear Collisions
journal, December 1966


Methane activation on Ni(111): Effects of poisons and step defects
journal, October 2005


Ab Initio Molecular Dynamics Calculations versus Quantum-State-Resolved Experiments on CHD 3 + Pt(111): New Insights into a Prototypical Gas–Surface Reaction
journal, March 2014


Projector augmented-wave method
journal, December 1994


Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface
journal, November 2013


Methane dissociation on Pt(111): Searching for a specific reaction parameter density functional
journal, January 2016


Effects of Lattice Motion on Dissociative Chemisorption: Toward a Rigorous Comparison of Theory with Molecular Beam Experiments
journal, November 2016


The dissociative chemisorption of methane on Ni(100) and Ni(111): Classical and quantum studies based on the reaction path Hamiltonian
journal, November 2013


Six-dimensional quantum dynamics study for the dissociative adsorption of DCl on Au(111) surface
journal, April 2014


Site-specific dissociation dynamics of H 2 /D 2 on Ag(111) and Co(0001) and the validity of the site-averaging model
journal, September 2015


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Methane Dissociation on Ni(111): A New Understanding of the Lattice Effect
journal, December 2009


DFT study of the water gas shift reaction on Ni(111), Ni(100) and Ni(110) surfaces
journal, February 2016


CO 2 Reduction on Transition Metal (Fe, Co, Ni, and Cu) Surfaces: In Comparison with Homogeneous Catalysis
journal, February 2012


Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH 4 on Pt(111)
journal, May 2016


Surface chemistry of carbon dioxide
journal, January 1996


Chemisorption of CO 2 on Nickel Surfaces
journal, October 2005


Mode- and Bond-Selective Chemistry on Metal Surfaces: The Dissociative Chemisorption of CHD 3 on Ni(111)
journal, March 2015


A time‐dependent approach to flux calculation in molecular photofragmentation: Vibrational predissociation of HF–DF
journal, January 1995


Quantum dynamics of water dissociative chemisorption on rigid Ni(111): An approximate nine-dimensional treatment
journal, April 2016


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Mode selective chemistry at surfaces
journal, February 2009


Density Functional Theory-Assisted Microkinetic Analysis of Methane Dry Reforming on Ni Catalyst
journal, May 2015


Reaction path Hamiltonian for polyatomic molecules
journal, January 1980


The dissociative chemisorption of methane on Ni(100): Reaction path description of mode-selective chemistry
journal, September 2011


Vibrational mode-selective chemistry: Methane dissociation on Ni(100)
journal, June 2010


Mechanistic Insights into CO 2 Activation via Reverse Water–Gas Shift on Metal Surfaces
journal, February 2015


Kinetic aspect of CO2 reforming of CH4 on Ni(111): A density functional theory calculation
journal, March 2007


DFT studies of dry reforming of methane on Ni catalyst
journal, November 2009


Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity
journal, January 2016


Communication: Enhanced dissociative chemisorption of CO 2 via vibrational excitation
journal, March 2016


The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces
journal, June 2015


Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Methane dissociation and adsorption on Ni(111), Pt(111), Ni(100), Pt(100), and Pt(110)-(1×2): Energetic study
journal, February 2010


Time-Dependent Wave Packet Approach to State-to-State Reactive Scattering and Application to H + O 2 Reaction
journal, January 1996


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


The dissociative chemisorption of methane on Ni(111): The effects of molecular vibration and lattice motion
journal, May 2013


CO2 dissociation on Ni(211)
journal, October 2009


Vibrationally Promoted Dissociation of Water on Ni(111)
journal, May 2014


Identification of the "Active Sites" of a Surface-Catalyzed Reaction
journal, September 1996


Computational Investigation of Thermochemistry and Kinetics of Steam Methane Reforming on Ni(111) under Realistic Conditions
journal, February 2009


Turning carbon dioxide into fuel
journal, July 2010

  • Jiang, Z.; Xiao, T.; Kuznetsov, V. L.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923
  • https://doi.org/10.1098/rsta.2010.0119

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Six dimensional quantum dynamics study for dissociative adsorption of H2 on Cu(111) surface
journal, August 1997


CH4 dissociation on metals: a quantum dynamics model
journal, November 1991


Dynamics of the dissociative adsorption of CO2 on Ni(100)
journal, March 1986


Dissociative chemisorption of methane on metal surfaces: Tests of dynamical assumptions using quantum models and ab initio molecular dynamics
journal, August 2014


DFT Study of the Water–Gas Shift Reaction and Coke Formation on Ni(111) and Ni(211) Surfaces
journal, September 2012


State-resolved probes of methane dissociation dynamics
journal, April 2009


First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111)
journal, June 2016


Dissociative Chemisorption of Methane on Ni and Pt Surfaces: Mode-Specific Chemistry and the Effects of Lattice Motion
journal, September 2014


Catalysis for CO2 conversion: a key technology for rapid introduction of renewable energy in the value chain of chemical industries
journal, January 2013


Role of Steps in N 2 Activation on Ru(0001)
journal, August 1999


Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction
journal, June 2016


    Works referencing / citing this record:

    Origin of Thermal and Hyperthermal CO 2 from CO Oxidation on Pt Surfaces: The Role of Post‐Transition‐State Dynamics, Active Sites, and Chemisorbed CO 2
    journal, May 2019


    Effects of surface motion and electron-hole pair excitations in CO 2 dissociation and scattering on Ni(100)
    journal, May 2018


    Dynamics in reactions on metal surfaces: A theoretical perspective
    journal, May 2019