The binding energies of NO–Rg (Rg = He, Ne, Ar) determined by velocity map imaging

Abstract

We report velocity map imaging measurements of the binding energies, D 0 , of NO-Rg (Rg = He, Ne, Ar) complexes. TheX state binding energies determined are 3.0 ± 1.8, 28.6 ± 1.7, and 93.5 ± 0.9 cm −1 for NO-He, -Ne, and -Ar, respectively. These values compare reasonably well with ab initio calculations. Because theÃ-X transitions were unable to be observed for NO-He and NO-Ne, values for the binding energies in theà state of these complexes have not been determined. Based on our X state value and the reportedÃ-X origin band position, theà state binding energy for NO-Ar was determined to be 50.6 ± 0.9 cm −1 .

Modelling excited states of weakly bound complexes with density functional theory

“…31 In particular, B3LYP-D3 calculations predicted a minimum energy structure with a Ar-N-O angle of 301, whereas high level calculations and experiment find the angle to be 01. [45][46][47] A further shallow minimum is predicted for a Ar-N-O angle of 1801, in agreement with experiment and previous calculations. [45][46][47] This is illustrated in Fig.…”

“…[45][46][47] A further shallow minimum is predicted for a Ar-N-O angle of 1801, in agreement with experiment and previous calculations. [45][46][47] This is illustrated in Fig. 7 that shows the interaction potential at the B3LYP-D2 level, which closely resembles the B3LYP-D3 one.…”

“…[45][46][47] A further shallow minimum is predicted for a Ar-N-O angle of 180 o , in agreement with experiment and previous calculations. [45][46][47] This is illustrated in Figure 7 that shows the interaction potential at the B3LYP-D2 level, which closely resembles the B3LYP-D3 one. Also shown is an analogous potential energy surface computed with B3LYP-D2 with modified (increased by a factor of 2 for nitrogen and oxygen) van der Waals radii.…”

Interaction of the NO 3pπ (C 2Π) Rydberg state with RG (RG = Ne, Kr, and Xe): Potential energy surfaces and spectroscopy

“…The calculatedC state D 0 values are generally in very good agreement with experiment, with the least good agreement being for NO-Xe, as expected, since these calculations employed the smallest basis set. Some of this disagreement could be related to the difficulty of establishing the dissociation energy of theX states, which are derived from those of theà state, 15,50,51 where there are quasibound levels past the dissociation limit, but it is clear from Table I that these complexes exert high demands on the quantum chemistry (level of theory and basis set). The good agreement of the appearance of the simulated spectra with the experimental ones does, however, suggest that the origins of theC state spectra have been observed in all cases: for NO-Xe, it was particularly noted that the origin may not have been observed in the experiment, 21 but the simulation confirms that it was.…”

“…For the D 0 value for thẽ X state, we take a value of 94 cm −1 , which is between the two most recent determinations of 93.8 ± 0.9 cm −1 (Ref. 50) and 95.4 ± 1.4 cm −1 (Ref. 51).…”