Time-dependent density-functional theory for molecular photoionization with noniterative algorithm and multicenter B-spline basis set: CS2 and C6H6 case studies

Stener, Mauro; Fronzoni, G.; Decleva, P.

doi:10.1063/1.1937367

Cited by 98 publications

(111 citation statements)

References 65 publications

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“…Experimentally, this effect has been studied by tunable circularly polarized synchrotron radiation utilizing different methods of angle-resolved photoelectron spectroscopy. Theoretically, the Continuum Multiple Scattering method with the local Xα exchange correlation (CMS-Xα) [21] and the time-dependent density functional theory (TDDFT) B-spline LCAO formalism [22] were used in those studies.…”

Section: Introductionmentioning

confidence: 99%

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

et al. 2017

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The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O, is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly-symmetric O 1s and F 1s electronic orbitals, which are localized on different molecular sites. The respective dichroic β1 and angular distribution β2 parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry β1 of up to about 9% for the K-shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter-and site-sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.

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Section: Introductionmentioning

confidence: 99%

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

et al. 2017

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“…Benzene has 15 occupied valence orbitals (MOs) including five doubly occupied and degenerated MOs, whereas L-ala and L-phe have 18 and 32 doubly occupied MOs, respectively. While the valence electronic configurations of L-ala and L-phe are simple labels of their orbital numbers due to their C 1 point group symmetry, the electronic configuration of benzene (D 6h ) is given by the present model as: Table 2 compares the vertical ionization energies for benzene in the valence region using various models including RHF/TZVP, OVGF/TZVP, LB94/TZ2P, and SAOP/TZ2P, with other theoretical calculations 45,53 and available experimental data. 53,[55][56][57] For benzene, the ionization energies generated by the SAOP/TZ2P model exhibit comparable accuracy of the more sophisticated ADC(3) and OVGF/TZVP models and agree well with the experiment in almost the entire valence spectrum.…”

Section: Vertical Ionization Energies and Spectramentioning

confidence: 99%

Intramolecular interactions of L‐phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules

Wang

Falzon

2010

J Comput Chem

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Intramolecular interactions between fragments of L-phenylalanine, i.e., phenyl and alaninyl, have been investigated using dual space analysis (DSA) quantum mechanically. Valence space photoelectron spectra (PES), orbital energy topology and correlation diagram, as well as orbital momentum distributions (MDs) of L-phenylalanine, benzene and L-alanine are studied using density functional theory methods. While fully resolved experimental PES of L-phenylalanine is not yet available, our simulated PES reproduces major features of the experimental measurement. For benzene, the simulated orbital MDs for 1e(1g) and 1a(2u) orbitals also agree well with those measured using electron momentum spectra. Our theoretical models are then applied to reveal intramolecular interactions of the species on an orbital base, using DSA. Valence orbitals of L-phenylalanine can be essentially deduced into contributions from its fragments such as phenyl and alaninyl as well as their interactions. The fragment orbitals inherit properties of their parent species in energy and shape (ie., MDs). Phenylalanine orbitals show strong bonding in the energy range of 14-20 eV, rather than outside of this region. This study presents a competent orbital based fragments-in-molecules picture in the valence space, which supports the fragment molecular orbital picture and building block principle in valence space. The optimized structures of the molecules are represented using the recently developed interactive 3D-PDF technique.

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“…Asymptotic angular expansions up to a maximum L angular momentum value of 20 for C 2 H 2 and 24 for C 2 H 4 and C 2 H 6 , which ensure complete convergence of the calculated cross-sections up to 40 arbitrary units of electron kinetic energy, have been used. Full details of the method have been documented previously (34,35). The value of the fitted parameters, such as χ 2 , α, and β, for various bond lengths is shown in the table.…”

Section: Methodsmentioning

confidence: 99%

From double-slit interference to structural information in simple hydrocarbons

Kushawaha

Patanen

Guillemin

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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Interferences in coherent emission of photoelectrons from two equivalent atomic centers in a molecule are the microscopic analogies of the celebrated Young's double-slit experiment. By considering inner-valence shell ionization in the series of simple hydrocarbons C 2 H 2 , C 2 H 4 , and C 2 H 6 , we show that double-slit interference is widespread and has built-in quantitative information on geometry, orbital composition, and many-body effects. A theoretical and experimental study is presented over the photon energy range of 70-700 eV. A strong dependence of the oscillation period on the C-C distance is observed, which can be used to determine bond lengths between selected pairs of equivalent atoms with an accuracy of at least 0.01 Å. Furthermore, we show that the observed oscillations are directly informative of the nature and atomic composition of the inner-valence molecular orbitals and that observed ratios are quantitative measures of elusive many-body effects. The technique and analysis can be immediately extended to a large class of compounds.coherent state and molecular photoemission | interference phenomena

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Time-dependent density-functional theory for molecular photoionization with noniterative algorithm and multicenter B-spline basis set: CS2 and C6H6 case studies

Cited by 98 publications

References 65 publications

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

Intramolecular interactions of L‐phenylalanine: Valence ionization spectra and orbital momentum distributions of its fragment molecules

From double-slit interference to structural information in simple hydrocarbons

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