A COMPARISON OF CAR-PARRINELLO AND BORN-OPPENHEIMER GENERALIZED VALENCE BOND MOLECULAR DYNAMICS

Abstract Two methods for performing ab initio molecular dynamics using a generalized valence bond electronic wave function are compared: the Car—Parrinello and Born—Oppenheimer approaches. These techniques differ in how they generate a new electronic wave function at each time step. In the Car—Parrinello scheme, the wave function parameters are propagated as classical degrees of freedom, while in the Born—Oppenheimer scheme the equations describing the wave function are solved at each time step. It is found that trajectories obtained utilizing the Born—Oppenheimer approach are both more accurate and less costly than their Car—Parrinello counterparts for wave functions expressed in terms of atom-centered basis sets.

[1]  Renata M. Wentzcovitch,et al.  First principles molecular dynamics of Li: Test of a new algorithm , 1991 .

[2]  U. Landman,et al.  Born-Oppenheimer dynamics using density-functional theory: Equilibrium and fragmentation of small sodium clusters , 1991 .

[3]  W. C. Swope,et al.  A computer simulation method for the calculation of equilibrium constants for the formation of physi , 1981 .

[4]  E. Carter,et al.  Full Configuration Interaction Molecular Dynamics of Na2 and Na3 , 1995 .

[5]  Chelikowsky,et al.  First-principles simulation of liquid silicon using Langevin dynamics with quantum interatomic forces. , 1994, Physical review. B, Condensed matter.

[6]  H. Schaefer.  Methods of Electronic Structure Theory , 1977 .

[7]  Mark E. Tuckerman,et al.  Reversible multiple time scale molecular dynamics , 1992 .

[8]  Wu,et al.  Ab initio molecular-dynamics simulations of Si clusters using the higher-order finite-difference-pseudopotential method. , 1994, Physical review. B, Condensed matter.

[9]  Emily A. Carter,et al.  Ab initio molecular dynamics with correlated molecular wave functions: Generalized valence bond molecular dynamics and simulated annealing , 1992 .

[10]  E. Carter,et al.  Orbital‐based direct inversion in the iterative subspace for the generalized valence bond method , 1995 .

[11]  Car,et al.  Unified approach for molecular dynamics and density-functional theory. , 1985, Physical review letters.

[12]  G. Ciccotti,et al.  Numerical Integration of the Cartesian Equations of Motion of a System with Constraints: Molecular Dynamics of n-Alkanes , 1977 .

[13]  E. Carter,et al.  Time-Reversible Multiple Time Scale ab Initio Molecular Dynamics , 1993 .

[14]  Arias,et al.  Ab initio molecular-dynamics techniques extended to large-length-scale systems. , 1992, Physical review. B, Condensed matter.

[15]  Emily A. Carter,et al.  Spin eigenstate-dependent Hartree—Fock molecular dynamics , 1992 .

[16]  Barnett,et al.  Born-Oppenheimer molecular-dynamics simulations of finite systems: Structure and dynamics of (H2O)2. , 1993, Physical review. B, Condensed matter.

[17]  E. Carter,et al.  O(N3) scaling of two‐electron integrals during molecular geometry optimization , 1994 .

[18]  Boustani,et al.  Systematic ab initio configuration-interaction study of alkali-metal clusters: Relation between electronic structure and geometry of small Li clusters. , 1987, Physical review. B, Condensed matter.