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Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Ryan P. Brady, Charlie Drury, S. N. Yurchenko, Jonathan Tennyson

2024Journal of Chemical Theory and Computation11 citationsDOIOpen Access PDF

Abstract

curves of yttrium oxide (YO) and carbon monohydride (CH) as examples of two-state systems, where YO is characterized by a strong NAC, while CH has a strong diabatic coupling. Rovibronic energies and wave functions are computed using a new diabatic module implemented in the variational rovibronic code Duo. We show that it is important to include both the diagonal Born-Oppenheimer correction and nondiagonal DDRs. We also show that the convergence of the vibronic energy calculations can strongly depend on the representation of nuclear motion used and that no one representation is best in all cases.

Topics & Concepts

DiabaticDiatomic moleculeAdiabatic processEquivalence (formal languages)MoleculePhysicsStatistical physicsQuantum mechanicsMathematicsPure mathematicsAdvanced Chemical Physics StudiesSpectroscopy and Quantum Chemical StudiesMolecular spectroscopy and chirality
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