Geometric Phase Effect in Thermodynamic Properties and in the Imaginary-Time Multi-Electronic-State Path Integral...

The geometric phase (GP) is a fundamental quantum effect arising from conical intersections (CIs), with profound consequences for vibronic energy levels. Standard imaginary-time path integral molecular dynamics (PIMD) based on the Born-Oppenheimer approximation does not account for the GP, potentially leading to significant errors in low-temperature thermodynamic properties. In this Perspective, we demonstrate that the multi-electronic-state path integral (MES-PI) formulation in imaginary time─developed in J. Chem. Phys. 2018, 148, 102319─naturally captures the GP effect through the electronic trace of the product of statistically weighted overlap matrices between successive imaginary-time slices. This crucial capability was already implicit in the benchmark MES-PIMD simulations in that foundational work. To isolate this topological effect from other nonadiabatic effects, we introduce a geometric signature matrix (for the CI) and a winding-number-induced phase factor, constructing an ad hoc GP-excluded MES-PI method. Comparing this ad hoc baseline against the rigorous MES-PI approach allows us to unambiguously quantify the impact of the GP on thermodynamic properties. While simpler approximations exist when only the ground electronic state is considered, MES-PIMD is the most general and accurate approach applicable to real complex systems, where the location and topology of CI seams are often not known a priori.