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The choice of the electronic representation in on-the-fly quantum dynamics iscrucial. The adiabatic representation is appealing since adiabatic states arereadily available from quantum chemistry packages. The nuclear wavepackets arethen expanded in a basis of Gaussian functions, which follow trajectories toexplore the potential energy surfaces and approximate the potential using alocal expansion of the adiabatic quantities. Nevertheless, the adiabaticrepresentation is plagued with severe limitations when conical intersectionsare involved: the diagonal Born-Oppenheimer corrections (DBOCs) arenon-integrable, and the geometric phase effect on the nuclear wavepacketscannot be accounted for unless a model is available. To circumvent thesedifficulties, the moving crude adiabatic (MCA) representation was proposed andsuccessfully tested in low energy dynamics where the wavepacket skirts theconical intersection. We assess the MCA representation in the case ofnon-adiabatic transitions through conical intersections. First, we show thatusing a Gaussian basis in the adiabatic representation indeed exhibits theaforementioned difficulties with a special emphasis on the possibility toregularize the DBOC terms. Then, we show that MCA is indeed able to properlymodel non-adiabatic transitions. Tests are done on linear vibronic couplingmodels for the bis(methylene) adamantyl cation and the butatriene cation.

philosophical transactions - royal society. mathematical, physical and engineering sciences/philosophical transactions - royal society. mathematical, physical and engineering sciences

The moving crude adiabatic alternative to the adiabatic representation in excited state dynamics