Two new electronic states of H2O and D2O have been identified in the energy range 84 000–88 000 cm−1 as three-photon resonances in four-photon ionization spectroscopy. Simulations of the rotational intensity distributions using asymmetric top three-photon line strength theory, and rotational analyses, characterize the states as B1 and A2. These Rydberg states are assigned to the excitations 4sa1 ← 1b1[Formula: see text] and 3d2 ← 1b1[Formula: see text] on the basis of equilibrium geometries, quantum defects, and the polarization dependence of their three-photon transition probabilities. The identification of the one-photon forbidden 1A2–1A1 transition, together with published vacuum ultraviolet (VUV) absorption spectra, permits a consistent assignment for all five members of the 3d ← 1b1 complex.The [Formula: see text] and [Formula: see text] states arc predissociatcd via both homogeneous and heterogeneous mechanisms. The homogeneous channel from the [Formula: see text] state shows a dramatic isotope effect, being about two orders of magnitude faster in H2O than from equivalent levels of D2O. The heterogeneous predissociation exhibits irregular vibronic and isotopic dependencies, which can be rationalized in terms of the intercessional role of accidental near resonances with levels of the heavily predissociated [Formula: see text] state. The (000) levels of the [Formula: see text] states of H2O and D2O show contrasting heterogeneous predissociation behaviour, which can be interpreted with a knowledge of the relevant potential energy surfaces and the electronic–rotational Coriolis interactions that couple the states.
Role of Rydberg States in the Photochemical Dynamics of Ethylene