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

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

Theoretical studies of photoexcitation and ionization in H_2O

Theoretical studies are reported of the complete dipole excitation and ionization spectrum in H_2O employing Franck–Condon and static‐exchange approximations. Large Cartesian Gaussian basis sets are used to represent the required discrete and continuum electronic eigenfunctions at the ground‐state equilibrium geometry, and previously devised moment‐theory techniques are employed in constructing the continuum oscillator‐strength densities from the calculated spectra. Detailed comparisons are made of the calculated excitation and ionization profiles with recent experimental photoabsorption studies and corresponding spectral assignments, electron impact–excitation cross sections, and dipole (e, 2e)/(e, e+ion) and synchrotron‐radiation studies of partial‐channel photoionization cross sections. The various calculated excitation series in the outer‐valence (1b(^−1)_1, 3a(^−1)_1, 1b(^−1)_2) region are found to include contributions from valence‐like 2b_2 (σ*) and 4a_1(γ*) virtual orbitals, as well as appropriate nsa_1, npa_1, nda_1, npb_1, npb_2, ndb_1, ndb_2, and nda_2 Rydberg states. Transition energies and intensities in the ∼7 to 19 eV interval obtained from the present studies are seen to be in excellent agreement with the measured photoabsorption cross section, and to provide a basis for detailed spectral assignments. The calculated (1b(^−1)_1)X(^ 2)B_1, (3a_1(^−1))^2A_1, and (1b_2(^−1))(^2)B_2 partial‐channel cross sections are found to be largely atomic‐like and dominated by 2p→kd components, although the 2b_2(σ*) orbital gives rise to resonance‐like contributions just above threshold in the 3a_1→kb_2 and 1b_2→kb_2 channels. It is suggested that the latter transition couples with the underlying 1b_1→kb_1 channel, accounting for a prominent feature in the recent high‐resolution synchrotron‐radiation measurements. When this feature is taken into account, the calculations of the three outer‐valence channels are in excellent accord with recent synchrotron‐radiation and dipole (e, 2e) photoionization cross‐sectional measurements. The calculated inner‐valence (2a_1(^−1)) cross section is also in excellent agreement with corresponding measured values, although proper account must be taken of the appropriate final‐state configuration‐mixing effects that give rise to a modest failure of the Koopmans approximation, and to the observed broad PES band, in this case. Finally, the origins of the various spectral features present in the measured 1a_1 oxygen K‐edge electron energy‐loss profile in H_2O are seen to be clarified fully by the present calculations

Biomimetic sulfide oxidation by the means of immobilized Fe(III)-5,10,15,20-tetrakis(pentafluorophenyl)porphin under mild experimental conditions

This paper describes the oxidation of inorganic sulfide to sulfate, minimizing the formation of elemental sulfur. The described catalytic reaction uses dilute hydrogen peroxide at nearly neutral pH values in the presence of a bioinspired, heterogenized, and commercial ferriporphin. A substantial increase of the percentage of sulfide converted to sulfate is obtained in comparison with the yields obtained when working with hydrogen peroxide alone. The biomimetic catalyst also proved to be a much more efficient catalyst than horseradish peroxidase. Accordingly, it could be suitable for large-scale applications. Further studies are in progress to drive sulfate yields up to nearly quantitative

Representation of a complex Green function on a real basis: I. General Theory

When the Hamiltonian of a system is represented by a finite matrix, constructed from a discrete basis, the matrix representation of the resolvent covers only one branch. We show how all branches can be specified by the phase of a complex unit of time. This permits the Hamiltonian matrix to be constructed on a real basis; the only duty of the basis is to span the dynamical region of space, without regard for the particular asymptotic boundary conditions that pertain to the problem of interest.Comment: about 40 pages with 5 eps-figure

Photoexcitation and ionization in molecular fluorine: Stieltjes–Tchebycheff calculations in the static-exchange approximation

Theoretical investigation of outer (1pig, 1piu, 3sigmag) and inner (2sigmau, 2sigmag) valence-shell electronic photoexcitation and ionization cross sections in molecular fluorine are reported employing separated-channel static-exchange calculations and Stieltjes–Tchebycheff (S–T) moment-theory techniques. The discrete vertical electronic 1pig excitation series are found to be in good agreement with recent spectral assignments and previously reported theoretical studies, and those for 1piu, 3sigmag, 2sigmau and 2sigmag excitations are in general accord with position and intensity estimates based on quantum-defect analysis. Certain of the partial-channel photoionization cross sections in F2 are seen to exhibit resonancelike features similar to those reported recently in related S–T studies of photoionization in N2, CO, and O2. The resonances can be attributed to valencelike and pre-Rydberg diabatic states that cross the outer limbs of appropriate Rydberg series and corresponding ionic-state potential curves as functions of internuclear coordinate, giving rise to large continuum transition intensities at the ground-state equilibrium internuclear separation. In contrast to the situation in N2, CO, and O2, however, there is no evidence of a resonance like sigma-->sigma* feature in the 3sigmag-->ksigmau photoionization channel in F2. Rather, this resonance in F2 appears as a strong N-->Vg transition below the 3sigmag ionization threshold, and the corresponding partial-channel photoionization cross section is seen to be structureless. Although experimental studies of partial-channel photoionization cross sections are apparently unavailable for comparison, the calculations reported here should provide reliable approximations to the dipole excitation/ionization spectra in F2, and are helpful in understanding and clarifying the dependences of photoionization spectra in light diatomic molecules on shell occupancy and equilibrium internuclear separation when compared with the results of previous studies of photoionization in N2, CO, and O2

Contrasting roles of SPARC-related granuloma in bacterial containment and in the induction of anti–Salmonella typhimurium immunity

The role of matricellular proteins in bacterial containment and in the induction of pathogen-specific adaptive immune responses is unknown. We studied the function of the matricellular protein secreted protein, acidic and rich in cysteine (SPARC/osteonectin) in the dissemination of locally injected Salmonella typhimurium and in the subsequent immune response. We show that SPARC was required for the development of organized acute inflammatory reactions with granuloma-like (GL) features and for the control of bacterial spreading to draining lymph nodes (DLNs). However, SPARC-related GL also inhibited dendritic cell (DC) migration to the DLNs and limited the development of adaptive immune response, thus conferring increased susceptibility to the pathogen. In SPARC-deficient mice, both DC migration and antigen-specific responses were restored against bacteria, leading to protective anti–S. typhimurium immunity. This highlights a new function of matricellular proteins in bacterial infection and suggests that initial containment of bacteria can have drawbacks

Pseudospectral Calculation of the Wavefunction of Helium and the Negative Hydrogen Ion

We study the numerical solution of the non-relativistic Schr\"{o}dinger equation for two-electron atoms in ground and excited S-states using pseudospectral (PS) methods of calculation. The calculation achieves convergence rates for the energy, Cauchy error in the wavefunction, and variance in local energy that are exponentially fast for all practical purposes. The method requires three separate subdomains to handle the wavefunction's cusp-like behavior near the two-particle coalescences. The use of three subdomains is essential to maintaining exponential convergence. A comparison of several different treatments of the cusps and the semi-infinite domain suggest that the simplest prescription is sufficient. For many purposes it proves unnecessary to handle the logarithmic behavior near the three-particle coalescence in a special way. The PS method has many virtues: no explicit assumptions need be made about the asymptotic behavior of the wavefunction near cusps or at large distances, the local energy is exactly equal to the calculated global energy at all collocation points, local errors go down everywhere with increasing resolution, the effective basis using Chebyshev polynomials is complete and simple, and the method is easily extensible to other bound states. This study serves as a proof-of-principle of the method for more general two- and possibly three-electron applications.Comment: 23 pages, 20 figures, 2 tables, Final refereed version - Some references added, some stylistic changes, added paragraph to matrix methods section, added last sentence to abstract

Electron-impact vibrational excitation of cyclopropane

We report a very detailed test of the ab initio discrete momentum representation (DMR) method of calculating vibrational excitation of polyatomic molecules by electron impact, by comparison of its results with an extensive set of experimental data, covering the entire range of scattering angles from 10∘ to 180∘ and electron energies from 0.4 to 20 eV. The DMR calculations were carried out by solving the two-channel Lippmann-Schwinger equation in the momentum space, and the interaction between the scattered electron and the target molecule was described by exact static-exchange potential corrected by a density functional theory (DFT) correlation-polarization interaction that models target’s response to the field of incoming electron. The theory is found to quantitatively reproduce the measured spectra for all normal modes, even at the difficult conditions of extreme angles and at low energies, and thus provides full understanding of the excitation mechanism. It is shown that the overlap of individual vibrational bands caused by limited experimental resolution and rotational excitation must be properly taken into account for correct comparison of experiment and theory. By doing so, an apparent discrepancy between published experimental data could be reconciled. A substantial cross section is found for excitation of the non-symmetric HCH twisting mode ν 4 of A′′1 symmetry by the 5.5 eV A′2 resonance, surprisingly because the currently accepted selection rules predict this process to be forbidden. The DMR theory shows that the excitation is caused by an incoming electron in an f-wave of A′2 symmetry which causes excitation of the non-symmetric HCH twisting mode ν 4 of the A′′1 symmetry and departs in p- and f-waves of A′′2 symmetry