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Restricted Open-shell Hartree–Fock
Restricted open-shell Hartree–Fock (ROHF) is a variant of Hartree–Fock method for open shell molecules. It uses doubly occupied molecular orbitals as far as possible and then singly occupied orbitals for the unpaired electrons. This is the simple picture for open shell molecules but it is difficult to implement. The foundations of the ROHF method were first formulated by Clemens C. J. Roothaan in a celebrated paper and then extended by various authors, see e.g. for in-depth discussions. As with restricted Hartree–Fock theory for closed shell molecules, it leads to Roothaan equations written in the form of a generalized eigenvalue problem :\mathbf \mathbf = \mathbf \mathbf \mathbf Where F is the so-called Fock matrix (which is a function of C), C is a matrix of coefficients, S is the overlap matrix of the basis functions, and \epsilon is the (diagonal, by convention) matrix of orbital energies. Unlike restricted Hartree–Fock theory for closed shell molecules, the form of ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Hartree–Fock Method
In computational physics and chemistry, the Hartree–Fock (HF) method is a method of approximation for the determination of the wave function and the energy of a quantum many-body system in a stationary state. The Hartree–Fock method often assumes that the exact ''N''-body wave function of the system can be approximated by a single Slater determinant (in the case where the particles are fermions) or by a single permanent (in the case of bosons) of ''N'' spin-orbitals. By invoking the variational method, one can derive a set of ''N''-coupled equations for the ''N'' spin orbitals. A solution of these equations yields the Hartree–Fock wave function and energy of the system. Especially in the older literature, the Hartree–Fock method is also called the self-consistent field method (SCF). In deriving what is now called the Hartree equation as an approximate solution of the Schrödinger equation, Hartree required the final field as computed from the charge distributi ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
