Diagonalization without Diagonalization: A Direct Optimization Approach for Solid-State Density Functional Theory

We present a novel approach to address the challenges of variable occupation numbers in direct optimization of density functional theory (DFT). By parameterizing both the eigenfunctions and the occupation matrix, our method minimizes the free energy with respect to these parameters. As the stationary conditions require the occupation matrix and the Kohn-Sham Hamiltonian to be simultaneously diagonalizable, this leads to the concept of ``self-diagonalization,'' where, by assuming a diagonal occupation matrix without loss of generality, the Hamiltonian matrix naturally becomes diagonal at stationary points. Our method incorporates physical constraints on both the eigenfunctions and the occupations into the parameterization, transforming the constrained optimization into an fully differentiable unconstrained problem, which is solvable via gradient descent. Implemented in JAX, our method was tested on aluminum and silicon, confirming that it achieves efficient self-diagonalization, produces the correct Fermi-Dirac distribution of the occupation numbers and yields band structures consistent with those obtained with SCF methods in Quantum Espresso.

Constructing Custom Thermodynamics Using Deep Learning

One of the most exciting applications of AI is automated scientific discovery based on previously amassed data, coupled with restrictions provided by the known physical principles, including symmetries and conservation laws. Such automated hypothesis creation and verification can assist scientists in studying complex phenomena, where traditional physical intuition may fail. Of particular importance are complex dynamic systems where their time evolution is strongly influenced by varying external parameters. In this paper we develop a platform based on a generalised Onsager principle to learn macroscopic dynamical descriptions of arbitrary stochastic dissipative systems directly from observations of their microscopic trajectories. We focus on systems whose complexity and sheer sizes render complete microscopic description impractical, and constructing theoretical macroscopic models requires extensive domain knowledge or trial-and-error. Our machine learning approach addresses this by simultaneously constructing reduced thermodynamic coordinates and interpreting the dynamics on these coordinates. We demonstrate our method by studying theoretically and validating experimentally, the stretching of long polymer chains in an externally applied field. Specifically, we learn three interpretable thermodynamic coordinates and build a dynamical landscape of polymer stretching, including (1) the identification of stable and transition states and (2) the control of the stretching rate. We further demonstrate the universality of our approach by applying it to an unrelated problem in a different domain: constructing macroscopic dynamics for spatial epidemics, showing that our method addresses wide scientific and technological applications.

D4FT: A Deep Learning Approach to Kohn-Sham Density Functional Theory

Kohn-Sham Density Functional Theory (KS-DFT) has been traditionally solved by the Self-Consistent Field (SCF) method. Behind the SCF loop is the physics intuition of solving a system of non-interactive single-electron wave functions under an effective potential. In this work, we propose a deep learning approach to KS-DFT. First, in contrast to the conventional SCF loop, we propose to directly minimize the total energy by reparameterizing the orthogonal constraint as a feed-forward computation. We prove that such an approach has the same expressivity as the SCF method, yet reduces the computational complexity from O(N^4) to O(N^3). Second, the numerical integration which involves a summation over the quadrature grids can be amortized to the optimization steps. At each step, stochastic gradient descent (SGD) is performed with a sampled minibatch of the grids. Extensive experiments are carried out to demonstrate the advantage of our approach in terms of efficiency and stability. In addition, we show that our approach enables us to explore more complex neural-based wave functions.