Efficient antisymmetrization algorithm for the partially correlated wave functions in the free complement-local Schrödinger equation method

2015

The free-complement (FC) method is a general method for solving the Schrödinger equation (SE): The produced wave function has the potentially exact structure as the solution of the Schrödinger equation. The variables included are determined either by using the variational principle (FC-VP) or by imposing the local Schrödinger equations (FC-LSE) at the chosen set of the sampling points. The latter method, referred to as the local Schrödinger equation (LSE) method, is integral-free and therefore applicable to any atom and molecule. The purpose of this paper is to formulate the basic theories of the LSE method and explain their basic features. First, we formulate three variants of the LSE method, the AB, HS, and H(T)Q methods, and explain their properties. Then, the natures of the LSE methods are clarified in some detail using the simple examples of the hydrogen atom and the Hooke's atom. Finally, the ideas obtained in this study are applied to solving the SE of the helium atom highly accurately with the FC-LSE method. The results are very encouraging: we could get the world's most accurate energy of the helium atom within the sampling-type methodologies, which is comparable to those obtained with the FC-VP method. Thus, the FC-LSE method is an easy and yet a powerful integral-free method for solving the Schrödinger equation of general atoms and molecules.

Free-complement local-Schrödinger-equation method for solving the Schrödinger equation of atoms and molecules: Basic theories and features

2015

Solving the Schrödinger equation of molecules by relaxing the antisymmetry rule: Inter-exchange theory

2015

The Schrödinger equation (SE) and the antisymmetry principle constitute the governing principle of chemistry. A general method of solving the SE was presented before as the free complement (FC) theory, which gave highly accurate solutions for small atoms and molecules. We assume here to use the FC theory starting from the local valence bond wave function. When this theory is applied to larger molecules, antisymmetrizations of electronic wave functions become time-consuming and therefore, an additional breakthrough is necessary concerning the antisymmetry principle. Usually, in molecular calculations, we first construct the wave function to satisfy the antisymmetry rule, "electronic wave functions must be prescribed to be antisymmetric for all exchanges of electrons, otherwise bosonic interference may disturb the basis of the science." Starting from determinantal wave functions is typical. Here, we give an antisymmetrization theory, called inter-exchange (iExg) theory, by dividing molecular antisymmetrizations to those within atoms and between atoms. For the electrons belonging to distant atoms in a molecule, only partial antisymmetrizations or even no antisymmetrizations are necessary, depending on the distance between the atoms. So, the above antisymmetry rule is not necessarily followed strictly to get the results of a desired accuracy. For this and other reasons, the necessary parts of the antisymmetrization operations become very small as molecules become larger, leading finally to the operation counts of lower orders of N, the number of electrons. This theory creates a natural antisymmetrization method that is useful for large molecules.

Solving the Schrödinger equation of atoms and molecules: Chemical-formula theory, free-complement chemical-formula theory, and intermediate variational theory

Kurokawa

2018

Chemistry is governed by the principle of quantum mechanics as expressed by the Schrödinger equation (SE) and Dirac equation (DE). The exact general theory for solving these fundamental equations is therefore a key for formulating accurately predictive theory in chemical science. The free-complement (FC) theory for solving the SE of atoms and molecules proposed by one of the authors is such a general theory. On the other hand, the working theory most widely used in chemistry is the chemical formula that refers to the molecular structural formula and chemical reaction formula, collectively. There, the central concepts are the local atomic concept, transferability, and from-atoms-to-molecule concept. Since the chemical formula is the most successful working theory in chemistry ever existed, we formulate our FC theory to have the structure reflecting the chemical formula. Our basic postulate is that as far as the SE is the principle of chemistry, its solutions for chemistry should have the structure that can be related to the chemical formulas. So, in this paper, we first formulate a theory that designs the wave function to reflect the structure of the chemical formula. We call this theory chemical formula theory (CFT). In the CFT, we place the valence ground and excited states of each atom at each position of the chemical formula of the molecule and let them interact using their free valences to form the ground and excited states of the molecule. The principle there is the variational principle so that the ground and excited states obtained satisfy the orthogonality and Hamiltonian-orthogonality relations. Then, we formulate the exact FC theory starting from the initial functions produced by the CFT. This FC theory is referred to as free-complement chemical-formula theory (FC-CFT), which is expected to describe efficiently the solution of the SE by the above reason. The FC-CFT wave function is modified from that of CFT. Since this modification is done by the exact SE, its analysis may give some insights to chemists that assist their chemistry. Thus, this theory would be not only exact but also conceptually useful. Furthermore, the intermediate theory between CFT and FC-CFT would also be useful. There, we use only integratable functions and apply the variational principle so that we refer to this theory as FC-CFT-variational (FC-CFT-V). It is an advanced theory of CFT. Since the variational method is straightforward and powerful, we can do extensive chemical studies in a reasonable accuracy. After finishing such studies, if we still need an exact level of solutions, we add the remaining functions of the FC-CFT and perform the exact calculations. Furthermore, when we deal with large and even giant molecules, the inter-exchange (iExg) theory for the antisymmetry rule introduced previously leads to a large simplification. There, the inter-exchanges between distant electron pairs fade away so that only Coulombic interactions survive. Further in giant systems, even an electrostatic description becomes possible. Then, the FC-CFT for exactly solving the SE would behave essentially to order N for large and giant molecular systems, though the pre-factor should be very large and must be minimized.