The electron paramagnetic resonance spectrum of NF(1Δ) in the gas phase

Multireference configuration interaction and coupled‐cluster calculations on the X3Σ−, a1Δ, and b1Σ+ states of the NF molecule

“…The a 1 Δ state of NF correlates to N ( 2 D; M L = ± 2) + F ( 2 P; M L = 0) fragments, with the following two leading equilibrium CASSCF configurations: | a 1 Δ〉∼0.69|(1σ 2 2σ 2 3σ 2 4σ 2 1π)(2π−2π)〉 or using vbL diagrams: Clearly, the bonding occurs along the molecule's σ‐frame in an analogous way as in the X 3 Σ − state, the difference being that the N atom now finds itself in its first excited 2 D state, 2.384 eV above the 4 S 56 or 2.430 (2.397) eV at the MRCI (+Q)/aug‐cc‐pVQZ level. The computed value of the dipole moment at the MRCI level is μ = 0.44 D, remaining practically unchanged when core correlation (0.47 D) or relativistic effects (0.44 D) are taken into account, in fair agreement with the experimental value of 0.37 ± 0.06 D 32.…”

“…The quenching rate constants of the excited states of NF have been investigated in detail by Setser and co‐workers 27; their work was extended by Schmidt 28 and by Manke et al 29. Radiative lifetimes were determined by several authors 12, 30, 31, while the Stark effect of NF (a 1 Δ) was measured by Curran et al 32 resulting in the determination of the dipole moment of this state, μ = 0.37 ± 0.06 D. Far‐IR laser magnetic resonance spectra of a 1 Δ have also been reported 33 complementing the work of Curran et al 32. Information on highly excited 3d/4d 1,3 Φ, 3p 1 Σ + , and 3p 1 Δ Rydberg states was obtained using multiphoton ionization spectroscopy 34.…”

Microwave spectroscopy of the NBr radical in the X 3Σ− state

“…These molecules have extensively been studied through their electronic transitions. High resolution spectroscopic studies of these molecules, however, were reported only for fluoride [1][2][3][4][5][6][7][8] and chloride [9][10][11][12][13] (X 3 ⌺ Ϫ ,a 1 ⌬,b 1 ⌺ ϩ ). Since the NX radical has two atoms with nonzero nuclear spins, its rotational spectrum shows complicated structure by the fine and the hyperfine interactions.…”

Microwave spectroscopy of the PBr radical in the XΣ−3 state

“…High resolution spectroscopic studies of nitrogen monohalides were also reported for NF, [1][2][3][4][5][6][7][8] NCl, [9][10][11][12][13] NBr, 14 and NI ͑Ref. Among them, nitrogen monohalide molecules have been extensively studied through their electronic transitions.…”