On the ground and electronically excited states of Na3O: Theory and experiment

Abstract

Na 3 O has been generated by reacting preformed sodium clusters with O 2 and N 2 O in a crossed beam pickup arrangement. This ''superalkali'' species was probed by photodepletion spectroscopy coupled with one-photon ionization mass spectroscopy to yield: ͑i͒ a first measure of visible/NIR region photodissociation cross sections showing several broad absorption features, ͑ii͒ a rough determination of the ground state dissociation energy (1.48Ϯ0.04 eV), as well as ͑iii͒ a remeasurement of the ionization potential (3.69Ϯ0.15 eV). The experimental investigations were supplemented by quantum chemical ab initio calculations employing coupled-cluster methods for ground and excited states of Na 3 O. Experiment and theory are in good agreement, allowing a tentative assignment of the Na 3 O depletion spectrum while providing further evidence for the computed D 3h ground state. Observed and calculated dipole-allowed electronic transitions are discussed in terms of the unusual electronic structure of this nominally one excess-electron species.

Photoelectron spectroscopy of the molecular anions, Li3O− and Na3O−

“…11 and 12) being measured for Li 3 O (3.69 eV (Ref. 13) is the most recent value for Na 3 O). The excited neutral states of Na 3 O and Li 3 O have been mapped by the experiments of Hampe et al 13 and Neukermans et al, 7 respectively.…”

“…[3][4][5][6][7][8] Moreover, the bond lengths of the neutral molecules and their cations are similar in both cases. The ionization potentials of Li 3 O and Na 3 O have been studied both experimentally and theoretically, [1][2][3][4][5][8][9][10][11][12][13][14][15][16] with a recent value of 3.55 eV (Refs. 11 and 12) being measured for Li 3 O (3.69 eV (Ref.…”

Effects of the Atomic Number of Alkali Atom and Pore Size of Graphyne on the Second Order Nonlinear Optical Response of Superalkali Salts of Graphynes OM3+@GYs– (M = Li, Na, and K)

“…These representative structural models of delocalized π-conjugated graphynes were chosen here to combine with superalkalis (OLi 3 , ONa 3 , and OK 3 ) to generate a new series of complexes. Note that these superalkalis have been experimentally synthesized, [38][39][40] and they can serve as basic building blocks for new complexes. [41][42][43][44] The evolution of their first hyperpolarizability with varying superalkali atom and pore size of graphyne has been analyzed in order to explore new high-performance NLO molecules.…”

Reaction Kinetics of Meteoric Sodium Reservoirs in the Upper Atmosphere

“…for sodium oxide clusters with 3 or more sodium atoms. 24,26,46 Due to the close to threshold ionisation, the observed progressions correspond most likely to parent ions. The observation of Na clusters results in part from the relatively high source Na concentrations required to enable observation of NaO and NaOH by PI-ToF, but also from their high ionisation efficiencies.…”

“…An important drawback of spectroscopic and chemical conversion techniques is that these target a single species at a time. Multiplexed observation of sodium oxides and hydroxides using mass spectrometry has been reported previously at high temperatures, in vaporisation, pick-up and crossed molecular beam arrangements, mainly in the context of thermochemical analysis and molecular electronic structure studies, [20][21][22][23][24][25][26][27][28] but the observation of sodium compound kinetics at thermal energies has remained elusive for mass spectrometric techniques.…”