CORRELATION ENERGY Meaning and
Definition
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Correlation energy is a term used in physics and chemistry to describe the portion of the total energy of a many-particle system that arises due to the electron-electron interactions that cannot be accounted for by the mean-field approximation. In other words, it represents the deviation of the true energy of a system from what would be predicted based solely on the Coulomb interactions between individual particles.
In quantum mechanics, the wavefunction of a many-electron system is often approximated by a single determinant, known as the Hartree-Fock wavefunction, which neglects electron-electron correlations. However, the true behavior of electrons is inherently correlated due to their indistinguishable nature and the presence of their mutual repulsion. The correlation energy is the additional contribution to the energy that arises due to these correlations, beyond what is captured in the Hartree-Fock approximation.
The calculation of correlation energy is a challenging task in theoretical chemistry and physics. It requires the use of more advanced electronic structure methods, such as post-Hartree-Fock methods, density functional theory, or many-body perturbation theory. Accurate determination of correlation energy is crucial for describing various chemical and physical phenomena, including the stability of molecules, the prediction of reaction rates, and the properties of materials.
Overall, correlation energy represents the electronic interactions that go beyond the simple Coulombic forces between individual electrons, providing a more accurate description of many-particle systems and allowing for more precise predictions of their behavior.
Etymology of CORRELATION ENERGY
The term "correlation energy" in the field of quantum chemistry has its etymology rooted in the concept of electron correlation.
In quantum systems, the behavior of electrons is described by wave functions, which represent the probability of finding an electron in a particular state. However, due to the Pauli exclusion principle, which states that no two electrons can occupy the same quantum state simultaneously, the description of electron correlation is necessary.
Electron correlation refers to the deviations from simple independent-particle behavior, where electrons are treated as if they do not interact with each other. In reality, electrons influence each other's behavior through their mutual electrostatic repulsion. This leads to a complex quantum mechanical phenomenon where the behavior of one electron is influenced by the behavior of all the others.
To describe this electron correlation, the concept of correlation energy was introduced.
