Recent Progress in Orbital-Free Density Functional Theory: Unlocking the Power of Electrons

Orbital-free density functional theory (OFDFT) has emerged as a powerful tool in computational chemistry and materials science, offering a unique perspective on the electronic structure and properties of complex systems. Unlike traditional density functional theory (DFT),which relies on the concept of orbitals, OFDFT utilizes a density-based representation that enables the direct computation of electron density and other properties without explicitly constructing orbitals. This simplified approach not only reduces computational complexity but also provides insights into the fundamental nature of chemical bonding and electronic correlations.

The origins of OFDFT can be traced back to the early days of quantum chemistry when Thomas and Fermi proposed a statistical model for the electron density of atoms. This model laid the foundation for the development of DFT, but it was not until the work of Hohenberg and Kohn in the 1960s that the theoretical framework for OFDFT was established. In their seminal paper, Hohenberg and Kohn proved that the ground-state energy of a system is a unique functional of the electron density, independent of the external potential that generates it. This theorem opened the door for the development of methods to calculate the ground-state energy and other properties directly from the electron density.

OFDFT offers several advantages over traditional DFT and other electronic structure methods:

Recent Progress In Orbital-free Density Functional Theory (Recent Advances In Computational Chemistry Book 6)

by David M. Whitacre

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• Reduced Computational Complexity: By eliminating the need to construct orbitals, OFDFT significantly reduces the computational cost of electronic structure calculations. This makes it possible to study larger systems and longer time scales than with conventional methods.
• Improved Accuracy: OFDFT can provide more accurate results for certain types of systems, particularly those with strong electronic correlations or localized electrons. This is because OFDFT explicitly includes the effects of Pauli exclusion and electronic correlations in the electron density.
• Simpler Physical Interpretation: The density-based representation of OFDFT provides a more intuitive understanding of electronic behavior. The electron density is a physical observable that can be directly related to experimental measurements and properties such as charge distributions, bonding, and reactivity.

OFDFT has found wide applications in various fields of science and engineering, including:

• Chemistry: OFDFT is used to study chemical bonding, reaction mechanisms, and the electronic properties of molecules and clusters. It has been applied to systems such as transition metal complexes, organic molecules, and biological systems.
• Materials Science: OFDFT is used to investigate the electronic structure and properties of materials such as metals, semiconductors, and insulators. It can be used to predict material properties such as conductivity, magnetism, and optical response.
• Nanotechnology: OFDFT is employed to study the electronic properties of nanostructures such as nanoparticles, nanotubes, and nanowires. It can provide insights into the size-dependent behavior and unique properties of these materials.
• Catalysis: OFDFT is used to model the structure and reactivity of catalytic surfaces. It can provide information about adsorption, desorption, and reaction mechanisms, helping in the design of more efficient catalysts.

In recent years, there has been significant progress in the development and application of OFDFT. Some of the latest advancements include:

• Development of New Functionals: New functionals have been developed that provide improved accuracy for a wider range of systems. These functionals include the non-interacting-v-interacting (NVI) functional, the reduced-density-matrix (RDM) functional, and the screened-Coulomb hybrid (SCH) functional.
• Extension to Excited States: OFDFT has been extended to compute excited-state energies and properties using the adiabatic connection method or the density functional configuration interaction (DFCI) approach.
• Applications to Complex Systems: OFDFT has been applied to study increasingly complex systems, including biological molecules, materials with topological insulators, and systems with strong electron correlation.

Orbital-free density functional theory has emerged as a powerful tool for studying the electronic structure and properties of complex systems. Its reduced computational complexity, improved accuracy, and simpler physical interpretation make it an attractive alternative to traditional DFT and other electronic structure methods. As research in OFDFT continues, we can expect to see even more exciting developments and applications in the years to come.

• Recent Advances in Orbital-Free Density Functional Theory
• Orbital-Free Density Functional Theory: Concepts and Applications
• Density Functional Theory: A Practical

Recent Progress In Orbital-free Density Functional Theory (Recent Advances In Computational Chemistry Book 6)

by David M. Whitacre

5 out of 5

Language	:	English
File size	:	16680 KB
Text-to-Speech	:	Enabled
Screen Reader	:	Supported
Enhanced typesetting	:	Enabled
Print length	:	464 pages

FREE