Langhoff, P. W. and Orel, A. E. and Rescigno, T. N. and McKoy, B. V. (1978) Photoabsorption in formaldehyde: Intensities and assignments in the discrete and continuous spectral intervals. Journal of Chemical Physics, 69 (10). pp. 4689-4705. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:20120801-134420974
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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 2b_2(n), 1b_1(π), 5a_1(σ), 1b_2, and 4a_1 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 2b_2(n) →nsa_1, npa_1, npb_2, and nda_2 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 a_1σ^∗ (CO), a_1σ^∗ (CH), and b_2σ^∗ (CH)/π_y^∗ (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 ^1A_1→^1B_1, ^1B_2, and ^1A_1 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 ^1B_1 and ^1B_2 components, and larger discrepancies apparently due to channel coupling are present in the ^1A_1→^1A_1 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 ka_1σ^∗ (CO) resonance in the (5a_1^(−1))^2A_1 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.
|Additional Information:||© 1978 American Institute of Physics. Received 13 June 1978. Online Publication Date: 11 August 2008. This work was performed under the auspices of the U. S. Department of Energy under Contract No. W-7405-Eng-48. One of us (B. V. M.) acknowledges the support provided by a grant from the National Science Foundation and another (P. W. L.) acknowledges the support provided by a grant from the Donors of the Petroleum Research Fund, administered by the American Chemical Society.|
|Subject Keywords:||FORMALDEHYDE, PHOTOIONIZATION, CROSS SECTIONS, ABSORPTION SPECTRA, HARTREE−FOCK METHOD, EXCITATION|
|Classification Code:||PACS: 31.15.-p, 33.80.Eh|
|Official Citation:||Photoabsorption in formaldehyde: Intensities and assignments in the discrete and continuous spectral intervals P. W. Langhoff, A. E. Orel, T. N. Rescigno, and B. V. McKoy J. Chem. Phys. 69, 4689 (1978); http://dx.doi.org/10.1063/1.436422|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||01 Aug 2012 22:03|
|Last Modified:||26 Dec 2012 15:47|
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