Aziz, Emad F.

Aziz, Saadullah G.

Bokarev, Sergey I.

Grell, Gilbert

Kühn, Oliver

Seidel, Robert

Winter, Bernd

Institutional Repository of the Freie Universität Berlin

Erratum: “Multi-reference approach to the calculation of photoelectron spectraincluding spin-orbit coupling” [J. Chem. Phys. 143, 074104 (2015)]Gilbert Grell, Sergey I. Bokarev, Bernd Winter, Robert Seidel, Emad F. Aziz, Saadullah G. Aziz, and OliverKühn  Citation: The Journal of Chemical Physics 145, 089901 (2016); doi: 10.1063/1.4961314 View online: http://dx.doi.org/10.1063/1.4961314 View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/145/8?ver=pdfcov Published by the AIP Publishing  Articles you may be interested in Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling J. Chem. Phys. 143, 074104 (2015); 10.1063/1.4928511  Perturbational treatment of spin-orbit coupling for generally applicable high-level multi-reference methods J. Chem. Phys. 141, 074105 (2014); 10.1063/1.4892060  On the R -dependence of the spin-orbit coupling constant: Potential energy functions of Xe 2 + by high-resolution photoelectron spectroscopy and ab initio quantum chemistry J. Chem. Phys. 128, 234306 (2008); 10.1063/1.2937133  On the simulation of photoelectron spectra in molecules with conical intersections and spin-orbit coupling:The vibronic spectrum of C H 3 S J. Chem. Phys. 127, 104309 (2007); 10.1063/1.2764052  Ab initio based study of the ArO − photoelectron spectra: Selectivity of spin–orbit transitions J. Chem. Phys. 112, 5852 (2000); 10.1063/1.481186    Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to  IP:  87.77.118.212 On: Fri, 11 Nov2016 07:55:31THE JOURNAL OF CHEMICAL PHYSICS 145, 089901 (2016)Erratum: “Multi-reference approach to the calculation of photoelectronspectra including spin-orbit coupling” [J. Chem. Phys. 143, 074104 (2015)]Gilbert Grell,1 Sergey I. Bokarev,1,a) Bernd Winter,2 Robert Seidel,2 Emad F. Aziz,2,3Saadullah G. Aziz,4 and Oliver Kühn11Institut für Physik, Universität Rostock, Albert-Einstein-Str. 23-24, 18059 Rostock, Germany2Helmholtz-Zentrum Berlin für Materialien und Energie, Methods for Material Development,Albert-Einstein-Strasse 15, 12489 Berlin, Germany3Department of Physics, Freie Universität zu Berlin, Arnimalle 14, 14159 Berlin, Germany4Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, Saudi Arabia(Received 27 July 2016; accepted 5 August 2016; published online 24 August 2016)[http://dx.doi.org/10.1063/1.4961314]In Ref. 1 we have presented a novel first principles approach to the calculation of photoelectron spectra (PES) and acomparison with the widely used sudden approximation (SA)2–4 has been performed. Two mistakes have been made in Ref. 1which are corrected in this erratum. First, within the SA the intensity of a transition is proportional to the absolute square of theDyson orbital (DO) normσ(Ek) ∝ ΨN−1F aˆΨNI 2 . (1)However, in Figs. 2 and 5 of Ref. 1, the DO norm was not squared. Second, Eq. (10) from the original publication contained atypo and should read DSAFI2=ΨN−1F ψel(k) dˆΨNI 2 ≈ ΨN−1F aˆΨNI 2 . (2)Taking the square alters the discussion on the applicability of the SA to the calculation of X-ray PES of transition metalcompounds. We emphasize that the main results of Ref. 1, i.e., the PES obtained via the numerical integration of the DO withthe ionized electron wave function, are not affected.The corrected SA PES are presented in Fig. 1 together with the full calculation results. In contrast to what is claimed inRef. 1, Fig. 1 shows that the SA predicts the intensities of all peaks with an accuracy that is comparable to the full calculation.FIG. 1. (Left panel) Calculated and experimental PES of the gas-phase water for 180 eV photon energy. (Right panel) Experimental (2M FeCl2 aqueous solution)and calculated (for the [Fe(H2O)6]2+ cluster) core PES for 925 eV photon energy.a)Electronic mail: sergey.bokarev@uni-rostock.de0021-9606/2016/145(8)/089901/2/$30.00 145, 089901-1 Published by AIP Publishing. Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to  IP:  87.77.118.212 On: Fri, 11 Nov2016 07:55:31089901-2 Grell et al. J. Chem. Phys. 145, 089901 (2016)Thus, the SA provides a good approximation to the full calculation of L-edge core PES of [Fe(H2O)6]2+ where the kinetic energyof the outgoing electron is quite high and all transitions have the same character, i.e., being ionizations from the 2p orbitals.Although the results obtained within the SA for the L-edge PES of [Fe(H2O)6]2+ are quite accurate, the SA should be usedwith caution. If the spectrum contains transitions involving DOs of different character, e.g., localized on metal and ligands, orthe kinetic energy of the outgoing electron is low, the applicability of the SA should be investigated on a case to case basis. Wewould like to stress that the protocol proposed in Ref. 1 that utilizes the numerical integration for the matrix elements allows usto obtain reliable intensities also in cases, where the widely used SA cannot be applied.We acknowledge financial support by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah (GrantNo. D-003-435), Deutsche Forschungsgemeinschaft (Grant No. KU952/10-1), and Collaborative Research Center 1109.1G. Grell, S. I. Bokarev, B. Winter, R. Seidel, E. F. Aziz, S. G. Aziz, and O. Kühn, J. Chem. Phys. 143, 074104 (2015).2R. Manne and T. Åberg, Chem. Phys. Lett. 7, 282 (1970).3B. T. Pickup, Chem. Phys. 19, 193 (1977).4T. Åberg, Phys. Rev. 156, 35 (1967). Reuse of AIP Publishing content is subject to the terms: https://publishing.aip.org/authors/rights-and-permissions. Downloaded to  IP:  87.77.118.212 On: Fri, 11 Nov2016 07:55:31

Erratum: “Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling” [J. Chem. Phys. 143, 074104 (2015)]

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Erratum: “Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling” [J. Chem. Phys. 143, 074104 (2015)]

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