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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Rotational Spectrum of NSF3 in the Ground and v5 = 1 Vibrational States: Observation of Q-Branch Perturbation-Allowed Transitions with Δ(k — l) — 0, ±3, ±6 and Anomalies in the Rovibrational Structure of the v5= 1 State
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Rotational Spectrum of NSF3 in the Ground and v5 = 1 Vibrational States: Observation of Q-Branch Perturbation-Allowed Transitions with Δ(k — l) — 0, ±3, ±6 and Anomalies in the Rovibrational Structure of the v5= 1 State

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The rotational spectrum of NSF3 in the ground and v5 = 1 vibrational states has been investigated in the centimeter-and millimeter-wave ranges. R-branch (J+ 1←J) transitions for J = 0, 1 and Q-branch rotational transitions for the v5 = 1 vibrational state have been measured by waveguide Fourier transform microwave spectroscopy in the range 8—26.5 GHz. The Q-branch transitions include 28 direct l-type doubling transitions (kl = +1, A1) (kl = +1, A2) with J≤ 62, and 108 direct l-type resonance transitions following the selection rule Δk = Δl = ±2 with J ≤ 60 and G = k — l ≤ 3, A process called "regional resonance" was observed in which a cluster of levels interacted strongly over a large range in J. This process led to the observation of 55 perturbation-allowed transitions following the selection rules Δ(k — l) = ±3, ±6. In particular, (kl = +1, A_+) (kl = -2, A_-), (kl = +4, A_+) (kl = +1, A_-), (kl = +2) (kl = -1), (kl = +3) (kl = 0), (kl — +2) (kl = —3), and (kl = +3) (kl = —3). The various aspects of the regional resonances are discussed in detail. An accidental near-degeneracy of the kl = 0 and kl = —4 levels at J = 26/27 led to the observation of perturbation-allowed transitions following the selection rule Δ(k—l) = ± 6 with (kl = +2) (kl = —4). A corresponding near-degeneracy between kl = — 1 and kl = —3 levels at J = 30/31 led to the detection of similar transitions, but with (kl = +3) (kl = —3). In the range 230—480 GHz, R-branch rotational transitions have been measured by absorption spectroscopy up to J = 49 in the ground-state and up to J = 50 in the v5 = 1 vibrational state. The transition frequencies have been analyzed using various reduced forms of the effective Hamiltonians. The data for the v5 = 1 vibrational state have been fitted successfully using two models up to seventh order with Δk = ±3 interaction parameters constrained (d_t constrained to zero, and ε to zero or to the ground-state value). On the other hand, reductions with the (Δk = ±1, Δl = -+2) interaction parameter q_(12) fixed to zero failed to reproduce the experimental data since the parameters defining the reduction transformation do not arise in the correct order of magnitude. The ground-state data have been analyzed including parameters up to fourth order constraining either parameters of the Δk = ± 3 interactions to zero (reduction A), or of the Δk = ±6 interactions to zero (reduction B). The unitary equivalence of the different parameter sets obtained is demonstrated for both vibrational states.

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