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

Abstract: 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.