The vt=1 Rovibrational Hamiltonian for C3v Symmetric Top Molecules Containing One Quadrupolar Nucleus: Reductions and Application to AsF3

Effective correlation-free reduced Hamiltonian for the νt(E), νn(A1) Coriolis-interacting states of C3v symmetric-top molecules

“…. s n Þ ð 3Þ This is the reason the molecular parameters may be highly correlated and cannot all be fitted independently (see for example [3][4][5][6][7]). The values of the free parameters s i can be fixed by constraining one or more spectroscopic parameter (i.e.…”

“…Their results were extended for the isolated m t (E) states to higher orders by Watson et al [2], who also discussed the relations among the various molecular parameters derived from the fits with the different constraints. The conclusions derived in [1,2] have been successfully applied in analyzes of a number of isolated m t (E) states (for example [3][4][5][6][7]). This paper is an extension of the results obtained in [1] for the m t (E), m n (A 1 ) Coriolis-interacting levels.…”

Hyperfine structure of rotational transitions of 14NF3 in the v4=1 vibrational state

“…The data were fitted in a multiple fitting approach using three reduced forms of the effective Hamiltonian (reduction Q, D, and QD) according to Lobodenko et al [2], Watson et al [3], and Harder [4] and the unitary equivalence of the parameter sets as introduced in [3,4] was demonstrated. In the analysis of the hyperfine structure of the related molecule AsF 3 (v 4 = 1) it was shown that the concept of multiple fitting can be extended to nuclear quadrupole coupling [5]. In this note we apply this method using all three possible reductions to the hyperfine data obtained for 14 NF 3 in the vibrational state v 4 = 1.…”

“…For several transitions the hyperfine structure of three lines could be completely resolved and in some cases only single lines were observed. The contribution to the splittings arises from zero order nuclear quadrupole coupling (decreasing with J) and from the (2, 2) interaction (constant contribution to kl = +1 and increasing contribution (with J) for G=|k À l| > 0).Fits were performed using a program described in [6], which constructs Hamiltonian matrices according to the matrix elements as given in [5,6]. We used frequencies of the rotational transitions which were included in the fit performed in [1], in this case with their hyperfine components.…”

“…Fits were performed using a program described in [6], which constructs Hamiltonian matrices according to the matrix elements as given in [5,6]. We used frequencies of the rotational transitions which were included in the fit performed in [1], in this case with their hyperfine components.…”