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The direct observation of non-adiabatic dynamics at conical intersections isa long-standing goal of molecular physics. Novel time-resolved spectroscopieshave been proposed which are sensitive to electronic coherences induced by thepassage of an excited state wavepacket through a region of conicalintersection. Here we demonstrate that inclusion of the geometric phase effect,and its manifestations, is essential for the correct description of thetransient electronic coherences that may or may not develop. For electronicstates of different symmetry, electronic coherences are suppressed by thegeometric phase. Conversely, for states of the same symmetry, appreciableelectronic coherences are possible, but their magnitude depends on both thetopography of and direction of approach to the conical intersection. Thesegeneral results have consequences for all studies of electronic coherences atconical intersections.

The role of geometric phase in the formation of electronic coherences at conical intersections