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60
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85034903427
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In Ref. 7, Fabricant et al. have suggested that a typical polarization anisotropy of [formula omitted] could, at most, contribute [formula omitted] to observed dipole moments in the formaldehyde system. The magnitude of this effect is slightly below the limits placed upon the precision of the present Stark measurements.
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61
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85034898105
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Ph.D. thesis, Massachusetts Institute of Technology
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(1986)
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Vaccaro, P.H.1
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118
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85034890384
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As can be readily demonstrated through the use of perturbation theory (Ref. 74), the Stark effect in a near prolate asymmetric rotor (e.g., formaldehyde) arises primarily as a result of interactions between the two levels comprising an asymmetry doublet. Since these eigenstates are initially of opposite parity, the field-induced partitioning of rovibronic character between them provides a means of producing the mixed parity states required for the manifestation of an electric dipole moment in a rotating molecular system (Refs. 5 and 37). Consequently, to lowest order, the Stark effects exhibited by the components of an asymmetry doublet should correspond to a single value for the dipole moment. This approximation breaks down, however, when higher order interactions involving adjacent rovibronic levels are taken into account.
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120
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85034903519
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In Refs. 17(c) and 17(d), ab initio calculations performed by van Dijk and co-workers have indicated that the [formula omitted] coupling elements for [formula omitted] are an order of magnitude smaller than those in [formula omitted] Furthermore, at the [formula omitted] rovibronic energies examined in the present study, the isoenergetic [formula omitted] states are coupled to the [formula omitted] dissociative continuum through a barrier (Ref. 19). The smaller tunnelling rates expected for the heavier deuterated species will therefore translate into narrower effective linewidths for the highly excited, lifetime-broadened [formula omitted] states. Since the strength of interaction between individual [formula omitted] and [formula omitted] rovibronic eigenstates are dominated by their effective separation in energy (Ref. 17), the reduced tunnelling propensity for [formula omitted] (i.e., narrower [formula omitted] linewidths) suggest a smaller probability for [formula omitted] mixing.
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