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| - Electronic Signatures of Large Amplitude Motions: Dipole Moments of VibrationallyExcited Local-Bend and Local-Stretch States of S0 Acetylene
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| - A one-dimensional local bend model is used to describe the variation of electronic properties of acetylene invibrational levels that embody large amplitude local motions on the S0 potential energy surface. Calculationsperformed at the CCSD(T) and MR-AQCC levels of theory predict an approximately linear dependence ofthe dipole moment on the number of quanta in either the local bending or local stretching excitation. In thelocal mode limit, one quantum of stretching excitation in one CH bond leads to an increase of 0.025 D in thedipole moment, and one quantum of bending vibration in the CCH angle leads to an increase of 0.068 D. Theuse of a one-dimensional model for the local bend is justified by comparison to the well-established polyadmodel which reveals a decoupling of the large amplitude bending from other degrees of freedom in the rangeof Nbend = 14−22. We find that the same one-dimensional large amplitude bending motion emerges fromtwo profoundly different representations, a one-dimensional cut through an ab initio, seven-dimensionalHamiltonian and the three-dimensional (𝓁 = 0) pure-bending experimentally parametrized spectroscopicHamiltonian.
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