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We investigate, in this paper, the Gaussian (G) function with odd powers of r, rxaybzc exp(−αr2), called the r-Gaussian or simply the rG function. The reason we investigate this function here is that it is generated as the elements of the complement functions (cf's) when we apply the free complement (FC) theory for solving the Schrödinger equation to the initial functions composed of the Gaussian functions. This means that without the rG functions, the Gaussian set of functions cannot produce the exact solutions of the Schrödinger equation, showing the absolute importance of the rG functions in quantum chemistry. Actually, the rG functions drastically improve the wave function near the cusp region. This was shown by the applications of the present theory to the hydrogen and helium atoms. When we use the FC-sij theory, in which the inter-electron function rij is replaced with its square s i j = r i j 2 that is integrable, we need only one- and two-electron integrals for the G and rG functions. The one-center one- and two-electron integrals of the rG functions are always available in a closed form. To calculate the integrals of the multi-centered rG functions, we proposed the rG-NG expansion method, in which an rG function is expanded by a linear combination of the G functions. The optimal exponents and coefficients of this expansion were given for N = 2, 3, 4, 5, 6, and 9. To show the accuracy and the usefulness of the rG-NG method, we applied the FC-sij theory to the hydrogen molecule. [ABSTRACT FROM AUTHOR]

The free-complement (FC) theory proposed for solving the Schrödinger equation of atoms and molecules highly accurately was applied to the calculations of the potential curves of the lower nine states of the Li2 molecule. The results were compared with the accurate experimental Rydberg–Klein–Rees potential curves available. They overlap completely with each other without any shift everywhere for all the states of Li2. At all the calculated points on the seven potential curves ranging between −14.83 and −15.00 hartree, the average difference was only 0.0583 kcal/mol and the maximum difference was only +0.165 kcal/mol. For the vertical excitation energies from the ground state curve to the seven excited states, the differences between theory and experiment were 0.000 645 eV in average and their maximum difference was −0.007 20 eV. The potential properties calculated with the FC theory also agreed well with the experimental values. These results show a high potentiality of the FC theory as a highly predictive quantum chemistry theory. For comparison, as an example of the Hartree–Fock based theory popular in modern quantum chemistry, we adopted the symmetry-adapted-cluster (SAC)-configuration-interaction (CI) theory using a highly flexible basis set. While the FC theory gave the absolute agreements with experiments, the SAC-CI potential curves compare reasonably well with experiments only after shifting-down of the SAC-CI curves by 5.727 kcal/mol. The differences in the excitation energies between SAC-CI and experiments were 0.004 28 eV on average, and the maximum difference was +0.109 67 eV. The SAC-CI results reported in 1985 were less accurate but still reasonable. [ABSTRACT FROM AUTHOR]

The scaling function g of the scaled Schrödinger equation (SSE) is generalized to obtain accurate solutions of the Schrödinger equation (SE) with the free complement (FC) theory. The electron–nuclear and electron–electron scaling functions, giA and gij, respectively, are generalized. From the relations between SE and SSE at the inter-particle distances being zero and infinity, the scaling function must satisfy the collisional (or coalescent) condition and the asymptotic condition, respectively. Based on these conditions, general scaling functions are classified into "correct" (satisfying both conditions), "reasonable" (satisfying only collisional condition), and "approximate but still useful" (not satisfying collisional condition) classes. Several analytical scaling functions are listed for each class. Popular functions riA and rij belong to the reasonable class. The qualities of many electron–electron scaling functions are examined variationally for the helium atom using the FC theory. Although the complement functions of FC theory are produced generally from both the potential and kinetic operators in the Hamiltonian, those produced from the kinetic operator were shown to be less important than those produced from the potential operator. Hence, we used only the complement functions produced from the potential operator and showed that the correct-class gij functions gave most accurate results and the reasonable-class functions were less accurate. Among the examined correct and reasonable functions, the conventional function rij was worst in accuracy, although it was still very accurate. Thus, we have many potentially accurate "correct" scaling functions for use in FC theory to solve the SEs of atoms and molecules. [ABSTRACT FROM AUTHOR]

The free complement (FC) theory for solving the scaled Schrödinger equation (SSE) was applied to the Li atom for calculating the exact wave functions, the energies, and the various properties of the ground doublet S and excited P states. The SSE is equivalent to the Schrödinger equation (SE) but does not have the divergence difficulty of the variational equation of the SE. Because the Li atom is a three-electron system, the variational exact FC calculations for solving the SSE are possible using the function g = 1 - exp(-γ r ) as the "correct" scaling function of the SSE. The "reasonable" scaling function g = r was also used as comparative calculations. We performed variational calculations to the order eight of the FC theory and could obtain essentially exact solutions of the SSE or SE with the "correct" g function of the FC theory. We report here the values of the exact energy, spin density, electron density, and electron-nuclear and electron-electron cusp values of the doublet S and P states. They agreed very well with the experimental values and the best theoretical values presented by Drake and collaborators. This is a simple example that the exact theory gives the exact solutions.

The potential energy curves (PECs) of the low-lying five 1 Σ + and 1 Π states (X 1 Σ + , C 1 Σ + , 3 1 Σ + , A 1 Π, and D 1 Π states) of a CH + molecule, an important interstellar molecule, were calculated by the free complement (FC) - local Schrödinger equation (LSE) theory with the direct local sampling scheme. The FC wave functions were constructed based on the chemical formula theory (CFT), whose local characters correspond to the covalent dissociations: C + ( 2 P°(s 2 p))) + H( 2 S) of the X 1 Σ + and A 1 Π states and the ionic dissociations: C( 1 D(s 2 p 2 )) + H + of the C 1 Σ + and D 1 Π states. All the calculated PECs were obtained with satisfying the chemical accuracy, i.e., error less than 1 kcal/mol, as absolute total energy of the Schrödinger equation without any energy shift. The spectroscopic data calculated from the PECs agreed well with both experimental and other accurate theoretical references. We also analyzed the wave functions using the inverse overlap weights proposed by Gallup et al. with the CFT configurations. For the X 1 Σ + and A 1 Π states, the covalent C + (sp 2 ) and C + (p 3 ) configurations played important roles for bond formation. In the small internuclear distances of the C 1 Σ + , D 1 Π, and 3 1 Σ + states, the covalent character was also dominant as a result of the electron charge transfer from C to H + . Thus, the present FC-LSE results not only are accurate but also can provide chemical understanding according to the CFT.

The free-complement (FC) theory proposed for solving the Schrödinger equation of atoms and molecules highly accurately was applied to the calculations of the potential curves of the lower nine states of the Li 2  molecule. The results were compared with the accurate experimental Rydberg-Klein-Rees potential curves available. They overlap completely with each other without any shift everywhere for all the states of Li 2 . At all the calculated points on the seven potential curves ranging between -14.83 and -15.00 hartree, the average difference was only 0.0583 kcal/mol and the maximum difference was only +0.165 kcal/mol. For the vertical excitation energies from the ground state curve to the seven excited states, the differences between theory and experiment were 0.000 645 eV in average and their maximum difference was -0.007 20 eV. The potential properties calculated with the FC theory also agreed well with the experimental values. These results show a high potentiality of the FC theory as a highly predictive quantum chemistry theory. For comparison, as an example of the Hartree-Fock based theory popular in modern quantum chemistry, we adopted the symmetry-adapted-cluster (SAC)-configuration-interaction (CI) theory using a highly flexible basis set. While the FC theory gave the absolute agreements with experiments, the SAC-CI potential curves compare reasonably well with experiments only after shifting-down of the SAC-CI curves by 5.727 kcal/mol. The differences in the excitation energies between SAC-CI and experiments were 0.004 28 eV on average, and the maximum difference was +0.109 67 eV. The SAC-CI results reported in 1985 were less accurate but still reasonable.