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note
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-. The electron binding energy spectra were obtained by subtracting the kinetic energy spectra from the detachment photon energies.
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26
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0001470765
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The final geometries of all complexes were optimized using density functional theory, the B3LYP exchange-correlation functional [A. D. Becke, J. Chem. Phys. 98, 5648 (1993)] and the TZVP+ basis set. The TZVP+ basis set was derived from the DFT-optimized TZVP basis set [N. Godbout, D. R. Salahub, J. Andzelm, and E. Wimmer, Can. J. Chem. 70, 560 (1992)] by addition of a diffuse s function to each H (exponent =0.0457), and diffuse s and p functions to O and S (exponents 0.0814 and 0.0481 on O, 0.0509 and 0.0342 on S).
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4143095330
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The exponents of the diffuse functions were obtained from an even-tempered extrapolation of the outer exponents of the original basis set. Frequency calculations were done to verify that the optimized geometries were stable points on the potential energy surface. We then obtained more accurate energies from single-point B3LYP calculations using the aug-cc-pVTZ basis set [R. A. Kendall, T. H. Dunning, Jr., and R. A. Harrison, J. Chem. Phys. 96, 6796 (1992)]
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Gaussian, Inc., Pittsburgh, PA
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-8 a.u. to insure accuracy. In order to locate the lowest dianion energy minima, ∼10 initial geometries of each complex were first optimized at low levels of theory (typically RHF/3- 21 + G*). Many of the initial geometries optimized to the same final structure, generally giving ∼3 geometries for use as input to the higher level optimizations. The geometries of the singly charged anions were optimized using the corresponding dianion geometries as starting points. We used GAUSSIAN98 [M. J. Frisch et al., Gaussian 98, Revision A: Gaussian, Inc., Pittsburgh, PA (1998)] for all of the computations.
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Gaussian 98, Revision A
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Frisch, M.J.1
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30
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57649166017
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note
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We define the theoretical vertical electron binding energy as the difference in total energy between the optimized dianion complex and the singly charged anion calculated at the dianion geometry. We define the adiabatic electron binding energy as the difference in energy between the optimized geometries of the dianion and singly-charged anion complexes.
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