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+, was replaced by a hydrogen atom to subtract the effect of the electrostatic hydrogen-bonding interaction. Only the positions of newly-introduced hydrogen atoms were optimized with RHF/3-21G*, and single point calculation was carried out with UHF/6-31G*, assuming a radical cation (S = 1/2, charge = +1). C1 symmetry was adopted in this calculation.
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67651211377
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The lowered LUMO is also produced using the positively charged tetrameric model (see Figure 4b).
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The lowered LUMO is also produced using the positively charged tetrameric model (see Figure 4b).
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67651228950
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In the PBC calculation, non-degenerate alpha- and beta-orbitals are observed near the highest occupied energy level. Although the limitation of one-electron approximation of the periodic UHF method with spin-only correlation is mentioned in the calculations of transition metal oxides,32a particularly in this calculation, the energetic relationship between the PBC-SOMO and split alpha- and beta-orbitals strongly implies an electron-correlation effect among these three orbitals attributed to CI (so-called nondynamical electron correlation effect).26
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