Reactions of Selenium and Oxygen. Matrix Infrared Spectra and Density Functional Calculations of Novel Se_xO_y Molecules

Abstract

Reactions of selenium and oxygen were performed using five different methods, and the products were trapped for matrix infrared spectroscopic study. Based on different chemistry, photolysis and annealing behavior, selenium and oxygen isotopic substitution, and DFT structure and frequency calculations, several new selenium oxides are characterized. In addition to SeO, SeO 2 , and SeO 3 , and the (Se 2 )(O 2 ) complex, the new molecules SeSeO, SeOO, Se 2 O 2 , and OSeOO are identified. Several isomers of Se 2 O 2 are accidentally almost degenerate; the species identified, which contains a three-membered ring with an exocyclic SedO unit, is one of the most stable. The OSeOO species is probably a planar cis chain isomer (C s symmetry), which is calculated to lie about 100 kJ/mol above the D 3h structure of SeO 3 .

The selenium oxygen clusters SeOn (n=1–5) and their anions: Structures and electron affinities

“…But for the SeO À , the DZP++ B3LYP method predict the most accurate values (722.6 cm À1 ), which is close to the experimental data (730 ± 25 cm À1 ) [10]. The values (746.7 cm À1 ) provided by B3PW91 methods is also reasonable agreement with [16]. For the SeO 3 , Brabson and Andrews [16] is based on the discharge experiment and get a weak band at 997 cm À1 , which is similar to the data provided by Brisdon and Ogden [43].…”

“…Available experimental fundamentals are also included for comparison. Comparing with the limited experimental values for SeO, Brabson et al [16] had obtained frequency of 909.1 cm À1 by Matrix infrared spectra, which is just above the 906.2 cm À1 gas fundamental studied by Barrow et al [12]. At the same time, Brabson et al also used the DFT prediction frequency of 912.4 cm À1 .…”

“…Characters are depended by structures, so more and more experimental and theoretical researches on the geometrical structures of selenium Oxygen clusters are carried out [10][11][12][13][14][15][16]. Snodgrass et al [10,11] studied the geometry structures, adiabatic electron affinities, dissociation energies and vibrational frequencies about SeO and SeO 2 by applying the technique of negative ion photoelectron (photodetachment) spectroscopy to their negative ions.…”

“…Ficalora et al [15] used mass spectrometric studies at high temperatures sublimation of SeO and SeO 3 . Brabson et al [16]obtained vibrational frequencies of Se x O y Molecules by Matrix Infrared Spectra and Density Functional Calculations. Havel et al [17] and Alberti et al [18] studied Laser desorption/ionisation and laser ablation of SeOn + and SeOn À by Time-of-flight mass spectrometry and ab initio calculations.…”

Theoretical studies on the electronic spectrum of selenium dioxide. Comparison with ozone and sulfur dioxide

“…[2] reported a similar, but not as accurate, geometry for the ground state. The calculated vibrational frequencies are slightly higher than the experimental values [25], and need to be scaled by a factor of about 0.95. Xu et al [2] listed ground state frequencies calculated by seven different functionals.…”