e., (12) and are
the matrix elements of the Hamiltonians, (13) and (14) respectively. Here, V(r) stands for an external potential. The proposed calculation procedure employs linearly independent multiple correction vectors for updating the one-electron wave function. The pth one-electron wave function in the Ath SD is updated by (15) where C j (j = 1, 2,…, L + N c ) and N c are the expansion coefficient and the number of correction vectors, respectively. The components of the correction vectors G μ,m A determine N c linearly independent correction functions ξ μ (r) which are defined as linear combinations of Gaussian basis functions as (16) Since the linearly independent correction vectors can be given arbitrarily, randomly chosen values are employed in the present study. A larger number of correction vectors N c realize a larger volume search space; however, the number of the linearly independent AZD8931 manufacturer vectors N c is restricted to the dimension of the space defined by the basis set used. Thus, we have a linear combination of L + N c SDs as the new N-electron wave function (17) where (18) Figure 1 illustrates the flow of the present calculation procedure. Unrestricted
Hartree-Fock (UHF) solutions for a target system are used for initial one-electron wave functions. The coefficients of Equation 17 are given by solving the generalized eigenvalue equations AG 14699 obtained by employing the variational principle applied to the total energy, and we can have a new N-electron wave function as a linear combination of L SDs as shown in Equation 17. Iteration of the above updating process for all the one-electron wave functions of all SDs increasing the number of the SDs’ L leads to an essentially exact numerical solution of the ground state. Bindarit in vitro Figure 1 Flow of the present algorithm. Applications to few-electron molecular systems Convergence from performances for searching for the ground state of a C atom
with the 6-31G** basis set are shown in Figure 2. The UHF solutions are adopted as initial states, and the number of employed SDs is 30. The steepest descent direction and acceleration parameter are adopted for the calculation using one correction vector (N c =1), and seven randomly chosen linearly independent correction vectors are added to the steepest descent correction to create a calculation with eight correction vectors (N c =8). An indispensable advantage of the multi-direction search over the single steepest descent direction search is clearly demonstrated. Although the steepest descent vector gives the direction with the largest gradient, it does not necessarily point toward the global energy minimum state. On the contrary, a linear combination of multiple correction vectors can be used to obtain the minimum energy state within the given space by adopting the variation principle. Figure 2 Effectiveness of multi-direction search on total energy convergence.