Solving the spectroscopic phase: imaging excited wave packets and extracting excited state potentials from fluorescence data

Abstract

We develop an inversion scheme for obtaining the signs of transition-dipole amplitudes from fluorescence line intensities. Using the amplitudes thus obtained we show how to extract highly accurate excited state potential(s) and the transition-dipole(s) as a function of inter-nuclear displacements. The same dipole amplitudes can also be used to extract the phase and amplitude of unknown time-evolving wave packets, in essentially a quantum non-demolition manner. The procedure, which is demonstrated for the A(¹∑⁺_u) and B(¹Π_u) states of the Na₂ molecule, is shown to yield reliable results even when we are given incomplete or uncertain data. We also demonstrate the success of our approach in extracting double minimum potentials. The inversion scheme is in principle applicable to any polyatomic molecule.