Geometric phase effects and wave packet dynamics on intersecting potential energy surfaces

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Abstract
The impact of the geometric phase on the time evolution of quantum‐mechanical wave packets is studied theoretically. Two model systems of coupled electronic potential energy surfaces are compared. One of them, the well‐known E×e Jahn–Teller system, comprises two conically intersecting surfaces, and the dynamics is subject to the geometric phase. The other system, describing the (E+A)×e Pseudo‐Jahn–Teller effect, comprises three intersecting surfaces and the dynamics is not subject to a geometric phase. Apart from the geometric phase, the coupling to the upper surface is verified to be negligible for low‐energy wave packet motion. Still, the geometric phase leads to a pronounced difference of low‐energy wave packet dynamics in both systems. Most significant is the phenomenon of destructive self‐interference of the two parts of the wave packet that encircle the conical intersection on opposite sides. The importance of the resulting different shape of the wave packet for a fs pump‐probe spectrum is pointed out.

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