Orbital-free effective embedding potential at nuclear cusps.
نویسندگان
چکیده
A strategy to construct approximants to the kinetic-energy-functional dependent component (v(t)[rho(A),rho(B)](r)) of the effective potential in one-electron equations for orbitals embedded in a frozen-density environment [Eqs. (20) and (21) in Wesolowski and Warshel, J. Phys. Chem. 97, (1993) 8050] is proposed. In order to improve the local behavior of the orbital-free effective embedding potential near nuclei in the environment, the exact behavior of v(t)[rho(A),rho(B)](r) at rho(A)-->0 and integralrho(B)dr=2 is taken into account. As a result, the properties depending on the quality of this potential are invariably improved compared to the ones obtained using conventional approximants which violated the considered exact condition. The approximants obtained following the proposed strategy and especially the simplest one constructed in this work are nondecomposable, i.e., cannot be used to obtain the analytic expression for the functional of the total kinetic energy.
منابع مشابه
Orbital-free effective embedding potential at nuclear cusp
A new approach to approximate the kinetic-energy-functional dependent component (vt[ρA, ρB ](~r)) of the effective potential in oneelectron equations for orbitals embedded in a frozen density environment (Eqs. 20-21 in [Wesolowski and Warshel, J. Phys. Chem. 97, (1993) 8050]) is proposed. The exact limit for vt at ρA −→ 0 and
متن کاملElectronic Structure Investigation of Octahedral Complex and Nano ring by NBO Analysis: An EPR Study
To calculation non-bonded interaction of the [CoCl6]3- complex embedded in nano ring, we focus on the single wall boron-nitride B18N18 nano ring. Thus, the geometry of B18N18 nano ring has been optimized by B3LYP method with EPR-II (Electron paramagnetic resonance) basis set and geometry of the [CoCl6]3- complex has been optimized at B3LYP method with Aldrich’s VTZ basis set and Stuttgart RSC 1...
متن کاملOrbital-Free Embedding Effective Potential in Analytically Solvable Cases
The effective embedding potential introduced by Wesolowski and Warshel [J. Phys. Chem., 97 (1993) 8050] depends on two electron densities: that of the environment (nB) and that of the investigated embedded subsystem (n A). In this work, we analyze this potential for pairs n A and nB , for which it can be obtained analytically. The obtained potentials are used to illustrate the challenges in tak...
متن کاملElectronic Structure Investigation of Octahedral Complex and Nano ring by NBO Analysis: An EPR Study
To calculation non-bonded interaction of the [CoCl6]3- complex embedded in nano ring, we focus on the single wall boron-nitride B18N18 nano ring. Thus, the geometry of B18N18 nano ring has been optimized by B3LYP method with EPR-II (Electron paramagnetic resonance) basis set and geometry of the [CoCl6]3- complex has been optimized at B3LYP method with Aldrich’s VTZ basis set and Stuttgart RSC 1...
متن کاملMechanism of nitrate reduction by Desulfovibrio desulfuricans nitrate reductase--a theoretical investigation.
The oxidative half-reaction of oxygen atom transfer from nitrate to an Mo(IV) complex has been investigated at various levels of theory. Two models have been used to simulate the enzyme active site. In the second, more advanced model, additional amino acid residues capable of significantly affecting the catalytic efficiency of the enzyme were included. B3LYP/6-31+G*, ONIOM, and orbital-free emb...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- The Journal of chemical physics
دوره 129 7 شماره
صفحات -
تاریخ انتشار 2008