Photoabsorption in formaldehyde: Intensities and assignments in the discrete and continuous spectral intervals

Abstract

Theoretical investigations of total and partial-channel photoabsorption cross sections in molecular formaldehyde are reported employing the Stieltjes–Tchebycheff (S–T) technique and separated-channel static-exchange (IVO) calculations. Vertical one-electron dipole spectra for the 2b2(n), 1b1(π), 5a1(σ), 1b2, and 4a1 canonical molecular orbitals are obtained using Hartree–Fock frozen-core functions and large basis sets of compact and diffuse normalizable Gaussians to describe the photoexcited and ejected electrons. The calculated discrete excitation spectra provide reliable zeroth-order approximations to both valence and Rydberg transitions, and, in particular, the 2b2(n) →nsa1, npa1, npb2, and nda2 IVO spectra are in excellent accord with recent experimental assignments and available intensity measurements. Convergent (S–T) photoionization cross sections in the static-exchange (IVO) approximation are obtained for the 15 individual partial channels associated with ionization of the five occupied molecular orbitals considered. Resonance features in many of the individual-channel photoionization cross sections are attributed to contributions from valencelike a1σ* (CO), a1σ* (CH), and b2σ* (CH)/πy* (CO) molecular orbitals that appear in the photoionization continua, rather than in the corresponding one-electron discrete spectral intervals. The vertical electronic cross sections for 1A1→1B1, 1B2, and 1A1 excitations are in generally good accord with previously reported CI (S–T) predictions of continuum orbital assignments and intensities, although some discrepancies due to basis-set differences are present in the 1B1 and 1B2 components, and larger discrepancies apparently due to channel coupling are present in the 1A1→1A1 cross section. Partial-channel vertical electronic cross sections for the production of the five lowest parent-ion electronic states are found to be in general agreement with the results of very recent synchrotron-radiation photoelectron branching-ratio measurements in the 20 to 30 eV excitation energy interval. Most important in this connection is the tentative verification of the predicted orderings in intensities of the partial- channel cross sections, providing support for the presence of a strong ka1σ* (CO) resonance in the (5a1−1)2A1 channel. Finally, the total vertical electronic cross sections for absorption and ionization are in general accord with photoabsorption measurements, photoionization–mass–spectrometric studies, and the previously reported CI (S–T) calculations. Although further refined calculations including vibrational degrees of freedom and autoionization line shapes are required for a more precise quantitative comparison between theory and experiment, the present study should provide a reliable zeroth-order account of discrete and continuum electronic dipole excitations in molecular formaldehyde.