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Title: Coupled-cluster interpretation of the photoelectron spectrum of Ag3−

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Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 8; Related Information: CHORUS Timestamp: 2016-12-26 02:54:01; Journal ID: ISSN 0021-9606
American Institute of Physics
Country of Publication:
United States

Citation Formats

Bauman, Nicholas P., Hansen, Jared A., and Piecuch, Piotr. Coupled-cluster interpretation of the photoelectron spectrum of Ag3−. United States: N. p., 2016. Web. doi:10.1063/1.4961455.
Bauman, Nicholas P., Hansen, Jared A., & Piecuch, Piotr. Coupled-cluster interpretation of the photoelectron spectrum of Ag3−. United States. doi:10.1063/1.4961455.
Bauman, Nicholas P., Hansen, Jared A., and Piecuch, Piotr. 2016. "Coupled-cluster interpretation of the photoelectron spectrum of Ag3−". United States. doi:10.1063/1.4961455.
title = {Coupled-cluster interpretation of the photoelectron spectrum of Ag3−},
author = {Bauman, Nicholas P. and Hansen, Jared A. and Piecuch, Piotr},
abstractNote = {},
doi = {10.1063/1.4961455},
journal = {Journal of Chemical Physics},
number = 8,
volume = 145,
place = {United States},
year = 2016,
month = 8

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4961455

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  • We use the scalar relativistic ionized equation-of-motion coupled-cluster approaches, correlating valence and semi-core electrons and including up to 3-hole-2-particle terms in the ionizing operator, to investigate the photoelectron spectrum of Au{sub 3}{sup −}. We provide an accurate assignment of peaks and shoulders in the experimental photoelectron spectrum of Au{sub 3}{sup −} for the first time.
  • Coupled-cluster calculations including effects of connected triple excitations have been performed on the ground state of and several electronic states of FeCl3. The vertical electron detachment energies closely correspond to the band energies of the photoelectron spectrum recently obtained by Yang et al. [Yang et al. J. chem. Phys., 119, 8311 (2003).], and thus provide a possible assignment of the spectrum.
  • An interpretation of the valence-band photoelectron spectrum for americium metal is attempted. This involves a bulk as well as a surface f/sup 6/..-->..f/sup 5/ photoionization process. The surface contribution is shifted by 0.6 eV relative to the bulk peak. Furthermore, the experimental peak at 1.8 eV is interpreted as originating from divalent americium atoms at the surface.
  • We report total and differential cross sections for photodetachment from negative ions using Dyson orbitals calculated from equation-of-motion coupled-cluster wave functions and free wave description of the detached electron. The energy dependence of the cross sections is reproduced well, however, the accuracy of absolute values varies. For F{sup -}, C{sup -}, NH{sub 2}{sup -}, and H{sup -}, the calculated cross sections are within the error bars from the experimental values, whereas the errors for Li{sup -} and OH{sup -} are about 20%. The largest errors are observed for O{sup -} and O{sub 2}{sup -} for which the calculated cross sectionsmore » differ from the experimental ones by factors of 3 and 2, respectively. Calculated anisotropy parameters for atomic anions exhibit too slow decrease, which suggests that the diffuseness of the computed Dyson orbitals is underestimated. Moreover, in the asymptotic region, the orbitals exhibit artifactual oscillations probably due to the limitations of Gaussian basis sets. The analysis of the trends in the experimental anisotropy parameters suggests that the interaction of the detached electron with the core, which is neglected in the present model, is important.« less
  • The gas-phase photoelectron spectrum of Re/sub 3/Cl/sub 9/ has been measured at ca. 800/sup 0/K. The first vertical ionization potential occurs at 8.85 eV. Results of a discrete variational Hartree-Fock-Slater calculation suggest that this ionization be attributed to a /sup 2/E'' state. Spin-orbit splitting of the first ionization band also supports this assignment. Charge density contributions to this orbital are distributed over the Re 5d, bridging Cl 3p, and axial Cl 3p orbitals in a 5:2:3 ratio. Remaining features in the photoelectron spectrum and the proposed orbital assignments are as follows: 9.80 eV, 22e''; 9.90 eV, 18a/sub 2/'', 12a/sub 2/',more » 40e'; 10.47 eV, 21e''; 10.83 eV, 39e', 17a/sub 2/'', 5a/sub 1/''; 11.09 eV, 28a/sub 1/', 20e'', 38e'; 11.83 eV, 16a/sub 2/'', 37e'; 12.21 eV, 11a/sub 2/', 36e'; 13.06 eV, 27a/sub 1/'; 13.39 eV, 15a/sub 2/'', 19e'', 26a/sub 1/'; 13.86 eV, 35e'. A unique feature of bonding in this complex is the great stability of 25a/sub 1/', the cluster sigma-bonding orbital. Chemically, this manifests itself in a trans effect at the vertices of the trinuclear cluster framework. To allow a fair comparison between Re/sub 3/Cl/sub 9/ and the well-studied Re/sub 2/Cl/sub 8//sup 2 -/ ion, a calculation of the latter complex's electronic structure was also performed. A detailed comparison of the valence orbitals in these two molecules follows. 25 references, 5 figures, 3 tables.« less