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Of course, with this aprotic/apolar solvent, the environmental effects are rather limited. Gas-phase test calculations have been peformed for II (oo) and II (cc). For the former, the CC distances in the gas phase are 3.725 Å instead of 3.731 Å in n -hexane. For the TD spectra of II (oo), the two first important vertical transitions are 347 nm (f = 0.08) and 302 nm (f = 0.36) in the gas phase but 346 nm (f = 0.12) and 305 nm (f = 0.54) in n -hexane. For the doubly closed structure, gas-phase simulations yield 444 nm (f = 0.26) and 360 nm (f = 0.94), whereas PCM provides 449 nm (f = 0.33) and 362 nm (f = 1.23). In short, bulk solvent effects seem to principally impact the oscillator strengths in the present case
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Of course, with this aprotic/apolar solvent, the environmental effects are rather limited. Gas-phase test calculations have been peformed for II (oo) and II (cc). For the former, the CC distances in the gas phase are 3.725 Å instead of 3.731 Å in n -hexane. For the TD spectra of II (oo), the two first important vertical transitions are 347 nm (f = 0.08) and 302 nm (f = 0.36) in the gas phase but 346 nm (f = 0.12) and 305 nm (f = 0.54) in n -hexane. For the doubly closed structure, gas-phase simulations yield 444 nm (f = 0.26) and 360 nm (f = 0.94), whereas PCM provides 449 nm (f = 0.33) and 362 nm (f = 1.23). In short, bulk solvent effects seem to principally impact the oscillator strengths in the present case.
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