ELECTRONIC SPECTROSCOPY OF THE A$^{1}A^{\prime\prime}-X^{1}A^{\prime}$ SYSTEM OF DCF

Abstract

To further investigate the Renner-Teller effect and excited state barriers to linearity and dissociation in the simplest singlet carbene, HCF, we measured fluorescence excitation spectra and lifetimes of the pure bending levels 2$_0^{n}$ and combination bands 1$_0^{1}$2$_0^{n}$ and 2$_0^{n}$3$_0^{1}$ in the A$^{1}A^{\prime\prime}$-X$^{1}A^{\prime}$ system of the deuterated isotopomer, DCF. The spectra were measured under jet-cooled conditions using a pulsed discharge source, and rotationally analyzed to yield precise values for the band origins and rotational constants. The derived A$^{1}A^{\prime\prime}$ state parameters are compared with our previous results for HCF, and with the predictions of $ab$ $initio$ electronic structure theory.