The electronic and spin properties of excited Se-O2 intermediates

A quantum chemical study of photochemical processes in the reaction Se + O2 → SeO2 with allowance for the spin orbit interaction

“…Therefore, as was previously considered [40], the intersection of the 1 B 2 term of SeO 2 dioxide with the 1 A 1 term of Se(O 2 ) peroxide and the subsequent intersection of the 1 A 1 term with 2 1 A″ 1 [ 1 D 2 ⋅a 1 Δ g ] and 3 [ 3 P j ⋅b 1 g + ∑ ] terms of SeOO superoxide can be one of the ROS formation channels (a 1 Δ g , b 1 g + ∑ ) due to the pre-dissociation of the 1 B 2 term of dioxide.…”

“…symmetry and the SeOO superoxocomplex of C s symmetry without allowance for SOI are given in [40]. It is shown that R ( Fundamental vibrational frequencies of the peroxocomplex v sym = 904 cm -1 , v asym = 631 cm -1 , v bend = 538 cm -1 and the corresponding intensities of 12.51 km/mol, 11.13 km/mol, 4.06 km/mol that we calculated differ from the vibrational frequencies for the superoxocomplex that, according to DFT/UB3LYP calculations, are v sym = 1119 (98.24) cm -1 , v asym = 532 (4.52) cm -1 , v bend = 336 cm -1 (0.12 km/mol).…”

Peculiarities of formation of hydroxonium ion and its small clusters

“…Besides the above-mentioned phenomena, a number of reactions occur in the low-temperature plasma at the height above 100 km, involving cations [О + , O 2 + , O 4 + , Н + , Н 2 + , OH + , НО 2 + , H 2 O + , (О 2 + -Н 2 О), Н 3 О + , (Н 3 О + -Н 2 О), (Н 3 О + -2Н 2 О), and (Н 3 О + -ОН)], anions (О -, О 2 -, О 3 -, Н -, and ОH -), neutral atoms (О and Н [2]) and molecules (Н 2 , О 2, and Н 2 О, their intermolecular interactions removing restrictions on deactivation or singlet oxygen generation [3][4][5]; О 3 ), free radicals (ОН and НО 2 yielding excited oxygen and Н 2 О 2 molecules [6] via recombination), exited atoms {O( 1 D 1 ) [7], O( 1 S 0 )}, and excited singlet oxygen O 2 ( 1 Δ g ) [8][9][10]. Furthermore, the Н 3 О + -n(Н 2 О) (n = 1-9) small clusters existing in the gas phase may distort the radio signals.…”

“…In particular, it has been demonstrated that the binding energy per water molecule increases from 27 kJ/mol in the (Н 2 О) 2 dimer to 35-40 kJ/mol in the (Н 2 О) 5 and (Н 2 О) 6 clusters, remaining constant in the larger clusters [17][18][19].…”