Vibrational Electronic-Thermofield Coupled Cluster (VE-TFCC) Theory for Quantum Simulations of Vibronic Coupling...

A vibrational electronic-thermofield coupled cluster (VE-TFCC) approach is developed to calculate thermal properties of non-adiabatic vibronic coupling systems. The thermofield (TF) theory and a mixed linear exponential ansatz based on second-quantized Bosonic construction operators are introduced to propagate the thermal density operator as a "pure state" in the Bogoliubov representation. Through this compact representation of the thermal density operator, the approach is basis-set-free and scales classically (polynomial) as the number of degrees of freedoms (DoF) in the system increases. The VE-TFCC approach is benchmarked with small test models and a real molecular compound (CoF₄^- anion) against the conventional sum over states (SOS) method and applied to calculate thermochemistry properties of a gas-phase reaction: CoF₃ + F^- → CoF₄^-. Results shows that the VE-TFCC approach, in conjunction with vibronic models, provides an effective protocol for calculating thermodynamic properties of vibronic coupling systems.