XMVB 2.0: A new version of Xiamen valence bond program

Xiamen valence bond (XMVB), which is an ab initio nonorthogonal valence bond program, has been progressively developed and refined during the last 25 years. As the release of XMVB 1.0 in 2004, a number of significant enhancements and improvements have been made to the program. As a consequence, a new version, XMVB 2.0, has been released and will be described in this article. In XMVB 2.0, the nonorthogonal orbital-based reduced density matrix approach for the valence bond (VB) theory is implemented, based on the second quantization scheme for nonorthogonal orbitals. The present article also describes the recently developed algorithms for orbital optimization in the VB self-consist field (VBSCF) method, in which the internal contraction of wave function is used for computing energy gradients. Moreover, several newly implemented ab initio VB methods, such as VBSCF(CAS), internally contracted VB second-order perturbation theory (icVBPT2), VB polarizable continuum model, VB effective fragment potential (VBECP), and density-functional-based VB, are briefly reviewed in this article. Finally, test calculations of several planar arenes, in which up to 18 active electrons are involved, are performed with XMVB 2.0. © 2014 Wiley Periodicals, Inc.

[1]  R. Mcweeny,et al.  A spin‐free form of valence bond theory , 1988 .

[2]  Wei Wu,et al.  Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. I. Hamiltonian matrix elements between internally contracted excited valence bond wave functions. , 2013, The Journal of chemical physics.

[3]  M. Temprado,et al.  Critically Evaluated Thermochemical Properties of Polycyclic Aromatic Hydrocarbons , 2008 .

[4]  W. Roth,et al.  Die Berechnung von Resonanzenergien; das MM2ERW‐Kraftfeld , 1991 .

[5]  Sason Shaik,et al.  Classical valence bond approach by modern methods. , 2011, Chemical reviews.

[6]  Yirong Mo,et al.  Bond-Distorted Orbitals and Effects of Hybridization and Resonance on C−C Bond Lengths , 1996 .

[7]  Huaiyu Zhang,et al.  Nonorthogonal orbital based n-body reduced density matrices and their applications to valence bond theory. III. Second-order perturbation theory using valence bond self-consistent field function as reference. , 2014, The Journal of chemical physics.

[8]  Linus Pauling,et al.  The Nature of the Chemical Bond and the Structure of Molecules and Crystals , 1941, Nature.

[9]  F. London,et al.  Wechselwirkung neutraler Atome und homöopolare Bindung nach der Quantenmechanik , 1927 .

[10]  Wei Wu,et al.  Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. IV. The automatic implementation of the Hessian based VBSCF method. , 2014, The Journal of chemical physics.

[11]  Zexing Cao,et al.  Chapter 6 - A spin–free approach for valence bond theory and its applications , 2002 .

[12]  Peifeng Su,et al.  VBEFP: a valence bond approach that incorporates effective fragment potential method. , 2012, The journal of physical chemistry. A.

[13]  Jorge Nocedal,et al.  On the limited memory BFGS method for large scale optimization , 1989, Math. Program..

[14]  Sason Shaik,et al.  VBPCM: A Valence Bond Method that Incorporates a Polarizable Continuum Model , 2004 .

[15]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[16]  David L. Cooper,et al.  Applications of spin-coupled valence bond theory , 1991 .

[17]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[18]  Wei Wu,et al.  Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. II. An efficient algorithm for matrix elements and analytical energy gradients in VBSCF method. , 2013, The Journal of chemical physics.

[19]  A. Faessler,et al.  Quasi-elastic electroproduction of charged $ \rho$ -mesons on nucleons , 2010 .

[20]  Wei Wu,et al.  An efficient algorithm for complete active space valence bond self‐consistent field calculation , 2013, J. Comput. Chem..

[21]  Sason Shaik,et al.  Valence bond perturbation theory. A valence bond method that incorporates perturbation theory. , 2009, The journal of physical chemistry. A.

[22]  R. Turner,et al.  Heats of Hydrogenation. I. Apparatus and the Heats of Hydrogenation of Bicyclo-[2,2,1]heptene, Bicyclo[2,2,1]heptadiene, Bicyclo[2,2,2]octene and Bicyclo[2,2,2]octadiene , 1957 .

[23]  Wei Wu,et al.  XMVB : A program for ab initio nonorthogonal valence bond computations , 2005, J. Comput. Chem..

[24]  Wei Wu,et al.  DFVB: A Density-Functional-Based Valence Bond Method. , 2012, Journal of chemical theory and computation.

[25]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[26]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[27]  J. H. van Lenthe,et al.  The valence-bond scf (VB SCF) method.: Synopsis of theory and test calculation of oh potential energy curve , 1980 .

[28]  Mark S. Gordon,et al.  An effective fragment method for modeling solvent effects in quantum mechanical calculations , 1996 .