A Dynamically Weighted Constrained Complete Active Space Ansatz for Constructing Multiple Potential Energy Surfaces Within the Anderson-Holstein Model

21 March 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


We derive and implement the necessary equations for solving a dynamically weighted, state-averaged constrained CASSCF(2,2) wavefunction describing a molecule on a metal surface. We show that a partial constraint is far more robust than a full constraint. We further calculate the system-bath electronic couplings that arise because, near a metal, there is a continuum (rather than discrete) number of electronic states. This approach should be very useful for simulating heterogeneous electron transfer going forward.


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