Restoring the Conical Intersection Topology using Convex Density Functional Theory

Abstract

Conical intersections are central to the description of photophysics and photochemistry. Nevertheless, in non-adiabatic molecular dynamics simulations, they are fundamentally challenging for single-reference electronic structure methods. Density functional theory (DFT) and its time-dependent extension (TDDFT) represent the most widely used theoretical approaches in physics, chemistry, and biology. However, the treatment of ground and excited states as separate problems leads to breakdowns in the topological structure of potential energy surfaces near conical intersections. In this work, we solve this long-standing issue by presenting Convex DFT, a framework that, by explicitly enforcing convexity of the variational problem within an appropriately defined subspace, guarantees a unique and continuous electronic solution across regions of degeneracies. We demonstrate that Convex DFT yields smooth and physically meaningful intersection seams by comparison with multireference wave function methods. In this way, we establish the method as a robust and computationally efficient DFT approach for treating electronically degenerate regions. These developments represent a critical step toward reliable non-adiabatic simulations beyond the limitations of conventional TDDFT.