Oxygen-assisted enhancement of H atom UV-photogeneration from hydrocarbons in van der Waals complexes RH–O2

Singlet oxygen photogeneration from X–O2 van der Waals complexes: double spin-flip vs. charge-transfer mechanism

“…Dependence of the O atom signal on stagnation-pressure and expanded mixture composition allowed the authors to infer a simple complex C 2 H 4 -O 2 to be a source of oxygen-enhanced photochemistry under the conditions similar to those used in the current work. 7 The images of complexes contain contributions of several dissociation channels with the kinetic energy of O atoms lower than the value of 0.19 eV for the dissociation of free O 2 . These channels are similar to those observed earlier.…”

“…[1][2][3][4][5][6][7] Besides a dramatic increase in oxygen atom photogeneration yield [1][2][3][4][5][6] new photodissociation channels giving rise to singlet oxygen have been observed. 5,6 These channels have been revealed on the basis of the analysis of the velocity map images of oxygen atoms ( 3 P j ) appearing after UV photoexcitation of complexes X-O 2 .…”

Calculations of the Geometry and Binding Energy of the Van Der Waals Complex of Ethylene With Oxygen C2h4-O2

“…ȼ ɤɪɢɨɝɟɧɧɵɯ ɤɢɫɥɨɪɨɞɧɵɯ ɦɚɬɪɢɰɚɯ ɧɚɛɥɸɞɚɸɬɫɹ ɩɪɨɰɟɫɫɵ ɮɨɬɨɨɤɢɫɥɟɧɢɹ ɨɪɝɚɧɢɱɟɫɤɢɯ ɦɨɥɟɤɭɥ ɩɪɢ ɮɨɬɨɜɨɡɛɭɠɞɟɧɢɢ ɤɨɧɬɚɤɬɧɵɯ ɤɨɦɩɥɟɤɫɨɜ X-O 2 ɜ ɩɨɥɨɫɚɯ ɩɨɝɥɨɳɟɧɢɹ, ɢɧɞɭɰɢɪɨɜɚɧɧɵɯ ɦɟɠɦɨɥɟɤɭɥɹɪɧɵɦ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟɦ [ 7 ]. ɂɞɟɚɥɶɧɨɣ ɦɨɞɟɥɶɸ ɞɥɹ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɢɡɭɱɟɧɢɹ ɜɥɢɹɧɢɹ ɫɥɚɛɨɫɜɹɡɚɧɧɨɝɨ ɨɤɪɭɠɟɧɢɹ ɧɚ ɮɨɬɨɮɢɡɢɤɭ ɢ ɮɨɬɨɯɢɦɢɸ ɤɢɫɥɨɪɨɞɚ ɹɜɥɹɸɬɫɹ ɜɚɧ-ɞɟɪɜɚɚɥɶɫɨɜɵ ɤɨɦɩɥɟɤɫɵ ɤɢɫɥɨɪɨɞɚ X-O 2 [8][9][10][11][12][13][14]. ɂɡɭɱɟɧɢɟ ɮɨɬɨɞɢɫɫɨɰɢɚɰɢɢ ɬɚɤɢɯ ɤɨɦɩɥɟɤɫɨɜ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɬɟɯɧɢɤɢ ɢɡɦɟɪɟɧɢɹ ɤɚɪɬ ɫɤɨɪɨɫɬɟɣ ɮɨɬɨɮɪɚɝɦɟɧɬɨɜ ɩɨɡɜɨɥɹɟɬ ɩɨɥɭɱɚɬɶ ɞɟɬɚɥɶɧɭɸ ɢɧɮɨɪɦɚɰɢɸ ɨ ɦɟɯɚɧɢɡɦɟ ɜɥɢɹɧɢɹ ɫɥɚɛɨɫɜɹɡɚɧɧɨɝɨ ɨɤɪɭɠɟɧɢɹ ɧɚ ɮɨɬɨɩɪɨɰɟɫɫɵ ɜ ɤɢɫɥɨɪɨɞɟ [8][9][10][11][12][13] ɢ ɜ ɦɨɥɟɤɭɥɚɯ X, ɩɚɪɬɧɟɪɚɯ ɩɨ ɤɨɦɩɥɟɤɫɭ [ 14 ], ɚ ɬɚɤɠɟ ɩɨɡɜɨɥɢɥɨ ɢɡɦɟ-ɪɢɬɶ ɷɧɟɪɝɢɸ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɨɣ ɫɜɹɡɢ ɜ ɪɹɞɟ ɤɨɦɩɥɟɤɫɨɜ X-O 2 [ 15 ].…”

“…ɗɬɨɬ ɤɨɦɩɥɟɤɫ ɹɜɥɹɟɬɫɹ ɨɞɧɢɦ ɢɡ ɧɚɢɛɨɥɟɟ ɢɫɫɥɟɞɨɜɚɧɧɵɯ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɵɯ ɤɨɦɩɥɟɤɫɨɜ ɤɢɫɥɨɪɨɞɚ X-O 2 . Ʉɪɨɦɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɨɝɨ ɢɫɫɥɟɞɨɜɚɧɢɹ ɮɨɬɨɩɪɨɰɟɫɫɨɜ ɜ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɨɦ ɤɨɦɩɥɟɤɫɟ C 2 H 4 -O 2 [ 9,14 ], ɛɵɥ ɢɫɫɥɟɞɨɜɚɧ ɫɩɟɤɬɪ ɩɨɝɥɨɳɟɧɢɹ ɜ ɤɢɫɥɨɪɨɞɟ, ɢɧɞɭɰɢɪɨɜɚɧɧɵɣ ɫɬɨɥɤɧɨɜɟɧɢɹɦɢ ɫ ɦɨɥɟɤɭɥɚɦɢ ɷɬɢɥɟɧɚ [ 3,16 ]. Ⱦɥɹ ɢɧɬɟɪɩɪɟɬɚɰɢɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɞɚɧɧɵɯ ɛɵɥɢ ɜɵɩɨɥɧɟɧɵ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɟ ɪɚɫɱɟɬɵ ɫɬɪɭɤɬɭɪɵ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɚ ɤɨɦɩɥɟɤɫɚ C 2 H 4 -O 2 [ 9 ].…”

“…ɗɧɟɪɝɢɸ ɫɜɹɡɢ (E bind ) ɦɟɠɞɭ ɦɨɥɟɤɭɥɚɦɢ ɷɬɢɥɟɧɚ (C 2 H 4 ) ɢ ɤɢɫɥɨɪɨɞɚ (Ɉ 2 ) ɜ ɜɚɧ-ɞɟɪ-ɜɚɚɥɶɫɨɜɨɦ ɤɨɦɩɥɟɤɫɟ C 2 H 4 -O 2 ɩɨ ɪɟɚɤɰɢɢ C 2 H 4 + Ɉ 2 o C 2 H 4 -O 2 ɪɚɫɫɱɢɬɵɜɚɥɢ ɫ ɭɱɟɬɨɦ ɨɲɢɛɤɢ ɫɭɩɟɪɩɨɡɢɰɢɢ ɛɚɡɢɫɚ (basis set superposition error, BSSE) ɜ ɪɚɦɤɚɯ ɭɪɚɜɧɨɜɟɲɢɜɚɸɳɟɝɨ ɦɟɬɨɞɚ (the counterpoise method) [ 20 ] ɢ ɷɧɟɪɝɢɢ ɧɭɥɟɜɵɯ ɤɨɥɟɛɚɧɢɣ (zero-point energy, ZPE). Ȼɵɥɢ ɩɪɨɚɧɚɥɢɡɢɪɨɜɚɧɵ ɞɜɟ ɫɯɟɦɵ ɪɚɫɱɟɬɚ ɷɧɟɪɝɢɢ ɫɜɹɡɢ: E bind ɢ E bind,BSSE [ 14,15 ]. ɋɯɟɦɚ 1.…”