Stark quantum beat spectroscopy of polyatomic molecules

We derive analytical expressions for Stark quantum beat signals of polyatomic molecules and discuss them with regard to molecular and geometrical parameters. The general treatment is specified for near prolate asymmetric rotor molecules and a method for determining rotational constants and all components of the dipole moment of electronically excited polyatomic molecules is presented. The method is tested and illustrated for the vibrationless S1 state of deuterated propynal (HCtriple bondCCDO, Cs symmetry) and its lowest frequency non-totally symmetric state 121. The results of the vibrationless state are compared with structural data reported in the literature. For the 121 state we obtain A=1.5004(43) cm-1, B=0.16131(34) cm-1, C=0.14623(34) cm-1, and the components of the electric dipole moment in the molecular plane μa=-0.88(2) D, μb=1.03(2) D. Furthermore, it is shown that the modulation depth of Stark quantum beat signals can be utilized to quantify the contribution of the individual components of the transition moment to the total emission. (orig.)