Self-consistent field theory functions

Olsen J and J0rgensen P 1995 Time-dependent response theory with applications to self-consistent field and multiconfigurational self-consistent field wave functions Modern Electronic Structure Theory vo 2, ed D R Yarkony (Singapore World Scientific) pp 857-990... 

Many problems in force field investigations arise from the calculation of Coulomb interactions with fixed charges, thereby neglecting possible mutual polarization. With that obvious drawback in mind, Ulrich Sternberg developed the COSMOS (Computer Simulation of Molecular Structures) force field [30], which extends a classical molecular mechanics force field by serai-empirical charge calculation based on bond polarization theory [31, 32]. This approach has the advantage that the atomic charges depend on the three-dimensional structure of the molecule. Parts of the functional form of COSMOS were taken from the PIMM force field of Lindner et al., which combines self-consistent field theory for r-orbitals ( nr-SCF) with molecular mechanics [33, 34]. 

J. Olsen and P. Jorgensen. Time-Dependent Response Theory with Applications to Self-Consistent Field and Multiconfigurational Self-Consistent Field Wave Functions, in Modern Electronic Structure Theory, edited by D. R. Yarkony, volume 2, chapter 13, pp. 857-990. World Scientific, Singapore, 1995. 

Anderson K, Malmqvist PA, Roos BO (1992) Second-order perturbation-theory with a complete active space self-consistent field reference function. J Chem Phys 96 1218... 

Nakano H (1993) Quasidegenerate perturbation theory with multiconfigurational self-consistent-field reference functions. J Chem Phys 99 7983... 

The density functional theory has the stmcture of a self-consistent field theory where the density profile is obtained from a simulation of a single chain in the... 

The obvious disadvantage of this simple LG model is the necessity to cut off the infinite expansion (26) at some order, while no rigorous justification of doing that can be found. In addition, evaluation of the vertex function for all possible zero combinations of the reciprocal wave vectors becomes very awkward for low symmetries. Instead of evaluating the partition function in the saddle point, the minimization of the free energy can be done within the self-consistent field theory (SCFT) [38 -1]. Using the integral representation of the delta functionals, the total partition function, Z [Eq. (22)], can be written as... 

Order Perturbation Theory with a Complete Active Space Self-Consistent Field Reference Function. 

K. Andersson, P. A. Malmqvist, and B. O. Roos,/. Chem. Phys., 96,1218 (1992). 2nd-Order Perturbation Theory with a Complete Active Space Self-Consistent Field Reference Function. 

The accurate calculation of these molecular properties requires the use of ab initio methods, which have increased enormously in accuracy and efficiency in the last three decades. Ab initio methods have developed in two directions first, the level of approximation has become increasingly sophisticated and, hence, accurate. The earliest ab initio calculations used the Hartree-Fock/self-consistent field (HF/SCF) methodology, which is the simplest to implement. Subsequently, such methods as Mpller-Plesset perturbation theory, multi-configuration self-consistent field theory (MCSCF) and coupled-cluster (CC) theory have been developed and implemented. Relatively recently, density functional theory (DFT) has become the method of choice since it yields an accuracy much greater than that of HF/SCF while requiring relatively little additional computational effort. 

Using a self-consistent field theory, Misra et al. [10] examined the effect of the brush charge, electrolyte concentration, and surface charge density on the brush thickness. They extended the self-consistent field polymer brush theory suggested by Milner et al. [11] to the case of a polyelectrolyte brush. The theory involves a parabolic monomer concentration profile rather than the step-function suggested by Alexander [12] and de Gennes [13,14], The repulsion force... 

Fig. 17. Phase diagram for intermediately segregated (%N=20) symmetric diblock (f=0.5) films confined between identical walls calculated from self-consistent field theory. The film thickness D is normalized by the bulk lamellar period Xb, and the ordinate AN is a measure of the surface field (which has the functional form H(z)=Aj (+cos(ti z/ )) bVN /e for 0

Andersson K, Malmqvist PA, Roos BO (1992) Second-order perturbation theory with a complete active space self-consistent field reference function. J Chem Phys 96 1218-1226 Tozer DJ, Amos RD, Handy NC, Roos BO, Serrano-Andres L (1999) Does density functional theory contribute to the understanding of excited states of unsaturated organic compounds Mol Phys 97 859-868... 

The relativistic theory and computation of atomic structures and processes has therefore attained some sort of maturity and the various codes now available are widely used. Those mentioned so far were based on ideas originating from Hartree and his students [28], and have been developed in much the same way as the non-relativistic self-consistent field theory recorded in [28-30]. All these methods rely on the numerical solution, using finite differences, of the coupled differential equations for radial orbital wave-functions of the self-consistent field. This makes them unsuitable for the study of molecules, for which it is preferable to expand the radial amplitudes in a suitably chosen set of analytic functions. This nonrelativistic matrix Hartree-Fock method, as it is often termed, was pioneered by Hall and Lennard-Jones [31], Hall [32,33] and Roothaan [34,35], and it was Roothaan s students, Synek [36] and Kim [37] who were the first to attempt to solve the corresponding matrix Dirac-Hartree-Fock equations. Kim was able to obtain solutions for the ground state of neon in 1967, but at the expense of some numerical instability, and it seemed at the time that the matrix Dirac-Hartree-Fock scheme would not be a serious competitor to the finite difference codes. 

Our multireference M0Uer-Plesset (MRMP) perturbation method [1-4] and MC-QDPT quasi-degenerate perturbation theory (QDPT) with multiconfiguration self-consistent field reference functions (MC-QDPT) [5,6] are perturbation methods of such a type. Using these perturbation methods, we have clarified electronic stmctures of various systems and demonstrated that they are powerful tools for investigating excitation spectra and potential energy surfaces of chemical reactions [7-10]. In the present section, we review these multireference perturbation methods as well as a method for interpreting the electronic structure in terms of valence-bond resonance structure based on the CASSCF wavefunction. 

Extension of reference wavefunctions—quasi-degenerate perturbation theory with quasi-complete active space self-consistent field reference functions (QCAS-QDPT) [35]... 

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