Research Article  Open Access
Ebru Çopuroğlu, "Evaluation of SelfFriction ThreeCenter Nuclear Attraction Integrals with Integer and Noninteger Principal Quantum Numbers over Slater Type Orbitals", Journal of Chemistry, vol. 2017, Article ID 1598951, 6 pages, 2017. https://doi.org/10.1155/2017/1598951
Evaluation of SelfFriction ThreeCenter Nuclear Attraction Integrals with Integer and Noninteger Principal Quantum Numbers over Slater Type Orbitals
Abstract
We have proposed a new approach to evaluate selffriction (SF) threecenter nuclear attraction integrals over integer and noninteger Slater type orbitals (STOs) by using Guseinov onerange addition theorem in standard convention. A complete orthonormal set of Guseinov exponential type orbitals (ETOs, ) has been used to obtain the analytical expressions. The overlap integrals with noninteger quantum numbers occurring in SF threecenter nuclear attraction integrals have been evaluated using auxiliary functions. The accuracy of obtained formulas is satisfactory for arbitrary integer and noninteger principal quantum numbers.
1. Introduction
It is well known that Roothaan openshell HartreeFock theory (HFR) and its extensions are not, in general, applicable to any state of a single configuration, which has any symmetry of open shells [1–10]. In a recent paper [11], Guseinov has eliminated the insufficiencies arising in HFR theory and has suggested a combined openshell HartreeFockRoothaan theory (CHFR) which includes the arbitrary number and symmetry of closed and openshell cases. It is clear that the evaluation of multicenter molecular integrals arising in CHFR theory has prime importance in many branches of physics particularly quantum physics, atomic and molecular physics, and nuclear physics. Using different approximations, considerable efforts have been made for calculating these integrals over STOs with noninteger principal quantum numbers (NISTOs). Notice that the NISTOs describe the physical systems more accurately than do ISTOs with integer principal quantum numbers [12–17]. But the main problem of using NISTOs basis in molecular calculations arises in the evaluation of the multicenter integrals. Various methods have been proposed in the literature for improving evaluation for the use of NISTOs in molecular calculations. It should be noted that most of the studies in the literature on the evaluation of multicenter molecular integrals with NISTOs were not entirely successful [18–20].
According to classical electrodynamics, the Lagrangian for a system of charges does not include the Lorentz selffriction (SF) potentials [21–23]. By considering this deficiency, Guseinov had suggested a new centrally symmetric potential of the SF field and on the basis of this idea Guseinov proposed the new complete orthonormal sets of ETOs. The indices arising from the use of total potential and occurring in the Guseinov ETOs are the frictional quantum number. For the evaluation of multicenter molecular integrals of integer Slater type orbitals (ISTOs) and noninteger Slater type orbitals (NISTOs) appearing in the CHFR approximation, Guseinov derived onerange addition theorems by the use of complete orthonormal sets of Guseinov ETOs [24].
In this case the analytical formulas for the evaluation of multicenter molecular integrals are directly depending on the SF quantum number. Thus, considering SF interactions, the calculation results of physical and chemical properties of atoms and molecules obtained from CHFR equations are closer to their real values. Therefore, the new type of multicenter molecular integrals arising in CHFR equations should be called SF multicenter molecular integrals. SF threecenter nuclear attraction integral is one of the most important molecular integrals arising in CHFR equations.
The aim of this paper is to provide the general analytical expressions of SF threecenter nuclear attraction integrals over ISTOs and NISTOs. With the help of Guseinov onerange addition theorems and ETOs, we have established new algorithm for calculating SF threecenter nuclear attraction integrals. We noticed that the SF threecenter nuclear attraction integrals are expressed in terms of twocenter overlap integrals and twocenter nuclear attraction integrals over NISTOs. The convergence, accuracy, and CPU time have been tested by our previous studies.
2. Definitions and Basic Formulas
The ISTOs can be written as follows [25, 26]:where is an integer principal quantum number, is the screening constant, and is a complex or real spherical harmonic (see [27–29] for exact definitions).
The NISTOs with noninteger values of the principal quantum number are defined byHere, is the gamma function.
To obtain the expansion of NISTO’s about a new center by the use of complete orthonormal sets of ETOs we can use the method for the expansion of ISTOs. Finally the formulas for the expansion of NISTOs in terms of ISTOs at a new origin are defined as [24]where , , and the coefficients are determined as follows:In (3) and (4), and the quantities are the overlap integrals between the NISTOs and ISTOs:
For the evaluation of overlap integrals we use the formula defined in terms of auxiliary functions [30]. As can be seen from (3), the coefficients for expansion of NISTOs for are expressed through the noninteger overlap integrals with the same screening constants defined by (5). It is clear that the obtained expansion formulas from this paper can also be used in the case of integer values of . Equation (3) becomes the series expansion formulas for translation of ISTOs (see, (5) of [31]).
3. Evaluation of SF ThreeCenter Nuclear Attraction Integrals
The SF threecenter nuclear attraction integrals over NISTOs are defined by where and .
Taking into account (3) in (6) we obtain the following relations:Here is the twocenter nuclear attraction integral over NISTOs determined by [32]
In order to calculate the twocenter nuclear attraction integrals we use the Laplace expansion of Coulomb potential. Then we find the following analytical expression for the twocenter nuclear attraction integrals: here , , and . See Appendix for exact formulas of , and quantities and functions occurring in (9). The quantities and in (9) are wellknown complete and incomplete gamma functions defined by, respectively, These functions have already been investigated by numerous authors with different algorithms (see, e.g., [33, 34] and references therein).
As can be seen from (7) and (9), by the use of Guseinov onerange addition theorems, the SF threecenter nuclear attraction integrals are expressed through the twocenter overlap integrals, gamma functions, auxiliary functions, and coefficients. The obtained formula is basic and valid for arbitrary integer and noninteger principal quantum numbers.
4. Numerical Results and Discussion
We have presented a new analytical method for the calculation of selffriction threecenter nuclear attraction integrals over STOs and NISTOs with the help of Guseinov onerange addition theorems. The computer programs of established formulas have been performed by using Mathematica 7.0 programming language in Intel (R) Core (TM) 2.5 GHz computer. On the basis of (7), the calculation results of SF threecenter nuclear attraction integrals over STOs and NISTOs have been given in Tables 1, 2, and 3. In Table 1, for and , the comparison results of SF threecenter nuclear attraction integrals over STOs and NISTOs have been presented. As can be seen from Table 1 our calculation results are satisfactory. Also, for different values of selffriction quantum number , the convergence of the series expansion relations of SF threecenter nuclear attraction integral over NISTOs as a function of summation limits of had been shown in Tables 2 and 3.



The coefficients , , and are repeatedly needed in a computation of the threecenter nuclear attraction integrals. We believe that a common storage scheme for the and coefficients and overlap integrals with the same selection rule, as proposed in this study, will give important contributions in reducing requirements of computer time for computation of multicenter integrals which arise in the HartreeFockRoothaan and Hylleraas approaches. For quick calculations, the and coefficients and integrals are stored in the memory of the computer. In order to put these coefficients and integrals into or to get them back from the memory, the positions of certain coefficients , , and integrals are determined by the following relations. For binomial coefficients For coefficients For overlap integrals
To demonstrate the effectiveness of storage method for given coefficients and integrals we calculated threecenter nuclear attraction integral with noninteger quantum numbers. The computer time required for the calculation of threecenter nuclear attraction integrals is not given in the tables due to the fact that the comparison cannot be made with the different computers used in the literature. For instance, for with sets , , , , , , , and CPU time takes about 5.897 ms and 2.57 ms by using usual and storage methods, respectively.
In Figure 1 we plot the convergence of the series (see (7)) of for with different values of parameter as a function of the indices . The series accuracy is shown in Figure 1 where the quantities are the values of integral for . As can be seen from Figure 1, for given , the convergence rates are satisfactory for arbitrary values of parameter . Greater accuracy is attainable by the use of more terms of expansions (7).
5. Conclusion
In conclusion, by considering selffriction effects, we have proposed an analytical efficient method for the calculation of threecenter nuclear attraction integrals over STOs and NISTOs using Guseinov onerange addition theorems. This allows us to take into account the selffriction field effect in atomic and molecular electronic structure evaluations.
Appendix
The generalized Gaunt coefficients and occurring in (9) are determined by the following relationships [32]:where See [32] for the exact definition of quantities and .
In this work is the complex or real spherical harmonics. The definition of phases for the complex spherical harmonics differs from the CondonShortley phases [27] by the sign factor and can be defined aswhereHere and .
Competing Interests
The author declares that they have no competing interests.
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Copyright © 2017 Ebru Çopuroğlu. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.