Computational methods that solve fundamental equations without empirical parameters.First-principles calculations are computational methods that solve the fundamental equations of physics — such as the Schrödinger equation or the Dirac equation — without fitting to experimental data or using empirical parameters. They aim to predict the properties of a system from scratch, using only the laws of quantum mechanics and the known constants of nature. This approach is powerful because it can describe materials, molecules, and even exotic systems like black branes without prior knowledge of their behavior, making it a cornerstone of modern computational physics and chemistry.
The field began in the 1920s with early quantum mechanical calculations on atoms, but it became practical in the 1960s after Walter Kohn and Pierre Hohenberg established the theoretical foundation of DFT, and later with the development of efficient algorithms in the 1980s and 1990s.
The most common implementation is density functional theory (DFT), which approximates the many-body quantum problem by focusing on electron density rather than individual wavefunctions. The equations are solved iteratively on a computer, often using a self-consistent field method: start with a guess for the electron density, compute the potential, solve for new wavefunctions, update the density, and repeat until convergence. For more exotic systems, such as black branes in holographic gravity, first-principles calculations may involve solving Einstein's equations numerically without assuming a specific solution form.
First-principles calculations are used to design new battery materials, predict the properties of catalysts, and simulate the behavior of matter under extreme conditions, such as in planetary interiors or inertial confinement fusion.
First-principles calculations can predict the existence of new materials before they are ever synthesized, guiding experimentalists toward promising candidates.









