Constructing accurate potential energy surfaces for a diatomic molecule interacting with a solid surface: H-2+Pt(111) and H-2+Cu(100)

By applying a corrugation-reducing procedure we have interpolated the six-dimensional (6D) potential energy surfaces for the H2/Pt(111) and H2/Cu(100) systems from data obtained by density functional theory (DFT) calculations. We have compared interpolated values with a large number of DFT results not used in the basis for the interpolation and we have obtained an average error below 20 meV and a maximum error of about 30 meV in the regions important for dissociative adsorption. Near the surface the corrugation-reducing procedure gives excellent results using only data from high-symmetry sites. However, we show that to reach the above mentioned accuracy level far from the surface, it is necessary to include information from at least one low-symmetry site. Care has been taken to demonstrate the quality of the interpolation along all degrees of freedom in different regions of the configuration space. The strengths of the method are shown together with the aspects requiring careful handling. A comparison wit...

[1]  G. Kroes.  Six-dimensional quantum dynamics of dissociative chemisorption of H2 on metal surfaces , 1999 .

[2]  Dmitrii E. Makarov,et al.  FITTING POTENTIAL-ENERGY SURFACES : A SEARCH IN THE FUNCTION SPACE BY DIRECTED GENETIC PROGRAMMING , 1998 .

[3]  E. Baerends,et al.  Quantum dynamics of the dissociation of H2 on Cu(100): dependence of the site-reactivity on initial rovibrational state. , 2000, Faraday discussions.

[4]  V. Szalay,et al.  Iterative and direct methods employing distributed approximating functionals for the reconstruction of a potential energy surface from its sampled values , 1999 .

[5]  J. H. Zhang,et al.  Quantum adsorption dynamics of a diatomic molecule on surface: Four‐dimensional fixed‐site model for H2 on Cu(111) , 1995 .

[6]  Eichler,et al.  Quantum Steering Effects in the Dissociative Adsorption of H2 on Rh(100). , 1996, Physical review letters.

[7]  J. Lennard-jones,et al.  Processes of adsorption and diffusion on solid surfaces , 1932 .

[8]  D. Hoffman,et al.  Interpolating distributed approximating functionals , 1998 .

[9]  G. Wolken,et al.  A model potential for chemisorption: H2+W(001) , 1975 .

[10]  Michael A. Collins,et al.  Learning to interpolate molecular potential energy surfaces with confidence: A Bayesian approach , 1999 .

[11]  E. Baerends,et al.  The effect of corrugation on the quantum dynamics of dissociative and diffractive scattering of H2 from Pt(111) , 2000 .

[12]  Steven D. Brown,et al.  Neural network models of potential energy surfaces , 1995 .

[13]  Construction of interpolated potential energy surfaces using constrained dynamics: Application to rotational inelastic scattering , 1999 .

[14]  Julius Jellinek,et al.  On the problem of fitting many-body potentials. I. The minimal maximum error scheme and the paradigm of metal systems , 1999 .

[15]  W. Dong,et al.  Representation of the 6D potential energy surface for a diatomic molecule near a solid surface , 2000 .

[16]  G. Kroes,et al.  Accuracy of trajectory methods for activated adsorption of H2 on Cu(100) , 1998 .

[17]  J. Light,et al.  Six dimensional quantum dynamics study for dissociative adsorption of H2 on Cu(111) surface , 1997 .

[18]  W. Dong,et al.  Six-dimensional classical dynamics of H2 dissociative adsorption on Pd(111) , 2000 .

[19]  E. J. Baerends,et al.  An analytical six-dimensional potential energy surface for dissociation of molecular hydrogen on Cu(100) , 1996 .

[20]  Axel Gross.  Reactions at surfaces studied by ab initio dynamics calculations , 1998 .

[21]  Matthias Scheffler,et al.  TRENDS IN THE CHEMICAL REACTIVITY OF SURFACES STUDIED BY AB INITIO QUANTUM-DYNAMICS CALCULATIONS , 1999 .

[22]  E. Baerends,et al.  Atomic and molecular hydrogen interacting with Pt(111). , 1999 .

[23]  M. Scheffler,et al.  Poisoning of Pd(100) for the dissociation of H2 : a theoretical study of co-adsorption of hydrogen and sulphur , 1995 .

[24]  E. Baerends,et al.  Erratum: Six-Dimensional Quantum Dynamics of Dissociative Chemisorption of (v=0,j=0)H2on Cu(100) [Phys. Rev. Lett. 78, 3583 (1997)] , 1998 .

[25]  W. Dong,et al.  H 2 dissociative adsorption on Pd(111) , 1997 .

[26]  L. Bengtsson,et al.  A first-principles potential energy surface for Eley–Rideal reaction dynamics of H atoms on Cu(111) , 1999 .

[27]  Donald J. Kouri,et al.  Distributed approximating functional approach to fitting multi-dimensional surfaces , 1996 .

[28]  Ab initio quantum and molecular dynamics of the dissociative adsorption of hydrogen on Pd(100) , 1997, cond-mat/9705102.

[29]  G. Wolken,et al.  Atomic recombination dynamics on solid surfaces: Effect of various potentials , 1977 .

[30]  J. Nørskov,et al.  Geometric and electronic factors determining the differences in reactivity of H2 on Cu(100) and Cu(111) , 1996 .

[31]  Georg Kresse,et al.  Dissociation and sticking of H 2 on the Ni(111), (100), and (110) substrate , 2000 .

[32]  E. Baerends,et al.  Six-dimensional quantum dynamics of dissociative chemisorption of (v=0, j=0) H2 on Cu(100). , 1997 .

[33]  H. Rabitz,et al.  Proper construction of ab initio global potential surfaces with accurate long-range interactions , 2000 .

[34]  White,et al.  Surface corrugation in the dissociative adsorption of H2 on Cu(100). , 1994, Physical review letters.

[35]  Matthias Scheffler,et al.  Ab initio based tight-binding Hamiltonian for the dissociation of molecules at surfaces , 1999 .

[36]  M. Persson,et al.  Eley-Rideal and hot-atom reaction dynamics of H(g) with H adsorbed on Cu(111) , 1997 .

[37]  Six-dimensional quantum dynamics of adsorption and desorption of H2 at Pd(100): Steering and steric effects. , 1995, Physical review letters.

[38]  E. Baerends,et al.  DISSOCIATION OF H2 ON CU(100) : DYNAMICS ON A NEW TWO-DIMENSIONAL POTENTIAL ENERGY SURFACE , 1995 .

[39]  Michael A. Collins,et al.  Application of interpolated potential energy surfaces to quantum reactive scattering , 1999 .

[40]  H. Rabitz,et al.  A general method for constructing multidimensional molecular potential energy surfaces from ab initio calculations , 1996 .

[41]  Scheffler,et al.  Multidimensional potential energy surface for H2 dissociation over Cu(111). , 1994, Physical review letters.

[42]  Donald J. Kouri,et al.  Distributed approximating functional approach to fitting and predicting potential surfaces. 1. Atom-atom potentials , 1996 .

[43]  S. Holloway,et al.  The dissociation of diatomic molecules at surfaces , 1995 .

[44]  T Hollebeek,et al.  Constructing multidimensional molecular potential energy surfaces from ab initio data. , 2003, Annual review of physical chemistry.

[45]  E. Baerends,et al.  A dynamical study of the chemisorption of molecular hydrogen on the Cu(111) surface , 1995 .

[46]  W. Dong,et al.  Role of orientational forces in nonactivated molecular dissociation on a metal surface , 2001 .