Infrared vibrational spectroscopy of cis-dichloroethene in Rydberg states

We have measured the infrared (IR) vibrational spectrum for cis-dichloroethene (cis-ClCH[Double Bond]CHCl) in excited Rydberg states with the effective principal quantum numbers n(*)=9, 13, 17, 21, 28, and 55 using the vacuum ultraviolet-IR-photoinduced Rydberg ionization (VUV-IR-PIRI) scheme. Although the IR frequencies observed for the vibrational bands nu(11) (*) (asymmetric C-H stretch) and nu(12) (*) (symmetric C-H stretch) are essentially unchanged for different n(*) states, suggesting that the IR absorption predominantly involves the ion core and that the Rydberg electron behaves as a spectator; the intensity ratio for the nu(11) (*) and nu(12) (*) bands [R(nu(11) (*)nu(12) (*))] is found to decrease smoothly as n(*) is increased. This trend is consistent with the results of a model ab initio quantum calculation of R(nu(11) (*)nu(12) (*)) for excited cis-ClCH[Double Bond]CHCl in n(*)=3-18 states and the MP26-311++G(2df,p) calculations of R(nu(11)nu(12)) and R(nu(11) (+)nu(12) (+)), where R(nu(11)nu(12))[R(nu(11) (+)nu(12) (+))] represents the intensity ratio of the nu(11)(nu(11) (+)) asymmetric C-H stretching to the nu(12)(nu(12) (+)) symmetric C-H stretching vibrational bands for cis-ClCH[Double Bond]CHCl (cis-ClCH[Double Bond]CHCl(+)). We have also measured the IR-VUV-photoion (IR-VUV-PI) and IR-VUV-pulsed field ionization-photoelectron depletion (IR-VUV-PFI-PED) spectra for cis-ClCH[Double Bond]CHCl. These spectra are consistent with ab initio calculations, indicating that the IR absorption cross section for the nu(12) band is negligibly small compared to that for the nu(11) band. While the VUV-IR-PIRI measurements have allowed the determination of nu(11) (+)=3067+/-2 cm(-1), nu(12) (+)=3090+/-2 cm(-1), and R(nu(11) (+)nu(12) (+)) approximately 1.3 for cis-ClCH=CHCl(+), the IR-VUV-PI and IR-VUV-PFI-PED measurements have provided the value nu(11)=3088.5+/-0.2 cm(-1) for cis-ClCH=CHCl.