Knowledge Bank

The effects of intense electric fields on two absorption bands of dimethylsulfide were investigated to determine the excited-state electronic symmetries, dipole moments, and mean polarizabilities. The bands studied were the vibrational series origins at 1959 {\AA} and 2284 {\AA}, the former of which has been assigned to the $4p\leftarrow n$ Rydberg transition and the latter to the $4s\leftarrow n$ Rydberg transition. The molecular orbital $n$ is the 3 p non-bonding orbital that is localized on the sulfur atom and the two carbon atoms. The data and its interpretation will be presented and will be shown to support the two Rydberg assignments from the standpoint of excited-state electronic symmetries. The changes from the ground-state value of the dipole moment were found to be decreases of $0.47\pm 0.03$ D and $0.42\pm 0.04$ D and the changes from the ground-state polarizability were found to be increases of $11.7+1.3\times 10-24cm3$ and $9.3\pm 2.0\times 10-24cm3$ for the $4p$ and $4s$ transitions, respectively.