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- W2025992253 abstract "The effect of rare gas complexation on the electronically excited S1(E′) state of triptycene (T), which is Jahn–Teller distorted, was investigated by two-color resonant two-photon ionization (2C-R2PI) spectroscopy of the supersonically cooled van der Waals complexes triptycene⋅Nen, n=1–3. These complexes afford unique possibilities to study the effects of weak intermolecular interactions on the intramolecular Jahn–Teller coupling. Since the atoms are adsorbed at high-symmetry positions, the system symmetry is lowered from D3h(n=0) to C2v for n=1 and 2, but reverts to D3h for n=3. A Jahn–Teller (A1⊕E)⊗e coupling model including a uniaxial external strain component was applied successfully to calculate the S1 state levels and S1←S0 electronic spectra of all three complexes. The spectrum of T⋅Ne3 was fully interpreted without inclusion of strain, implying a highly symmetric D3h structure in which each of the three V-shaped compartments of triptycene is occupied by a single Ne atom. In contrast, the vibronic spectra of T⋅Ne and T⋅Ne2 were fitted with a considerable uniaxial strain of −19.73 and 19.07 cm−1, respectively, confirming both the predicted C2v geometry of the complexes as well as the equal magnitude, but opposite sign of the intramolecular distortion induced by one or two Ne atoms. These distortions correspond to a small change of the angle of the V-shaped compartments by ∼0.8°. The spectra of T⋅Ne and T⋅Ne2 are much more complex compared to triptycene and T⋅Ne3 due to the splitting of the E vibronic levels in C2v symmetry, and the appearance of additional transitions to levels that are weak or symmetry forbidden in bare triptycene. The calculated Jahn–Teller potential energy surfaces and vibronic wave functions are discussed and classified in terms of their symmetry and localization/delocalization properties." @default.
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- W2025992253 date "1994-01-15" @default.
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- W2025992253 title "Intermolecular perturbation of a Jahn–Teller system: The triptycene⋅Ne<i>n</i> (<i>n</i>=1–3) van der Waals clusters" @default.
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- W2025992253 doi "https://doi.org/10.1063/1.466567" @default.
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