Spectroscopic density-matrix imaging and potential inversion: the rotational effect

Abstract

We further develop our methods of imaging of complex nonstationary wavefunctions and excited-state potentials [J. Chem. Phys. 103 (1995) 1748], by considering rotational effects. The wavefunction imaging method uses both frequency-resolved and time-resolved fluorescence data to derive the phase of the complex wavepacket emitting the radiation. The case of unpolarized density-matrices is considered, and explicit formulae for the extraction of the angular and radial dependence of the excited-state density matrices are developed. The procedure is demonstrated in Na 2 for excited-state density-matrices created by ultra-short pulse excitations, and for excited-state effective potentials of highly rotating molecules. An accurate inversion of the Na 2 (B 1 Π u ) potential, for a molecule whose angular momentum is as high as j = 133, is performed.