RETRACTED: 'Theoretical study of electronic properties and isotope effects in the UV absorption spectrum of disulfur'
| Autor: | Karolis Sarka, Shinkoh Nanbu, Sebastian O. Danielache, Alexey Kondorskiy |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
010304 chemical physics
010504 meteorology & atmospheric sciences Absorption cross section Ab initio General Physics and Astronomy Configuration interaction 01 natural sciences chemistry.chemical_compound chemistry Excited state 0103 physical sciences Kinetic isotope effect Disulfur Isotopologue Molecular orbital Atomic physics Physical and Theoretical Chemistry 0105 earth and related environmental sciences |
| Zdroj: | Chemical Physics. 508:61 |
| ISSN: | 0301-0104 |
| DOI: | 10.1016/j.chemphys.2018.05.007 |
| Popis: | The electronic structures of triplet S2 ground and excited states are studied by ab initio molecular orbital and configuration interaction calculation. Potential energy curves correlated with S ( 3 P ) + S ( 3 P ) and S ( 3 P ) + S ( 1 D ) at the dissociation limit are evaluated, and electronic terms for a total of 11 states are assigned. Transition dipole moments, as a function of internuclear distance, are determined for two allowed transitions to B ″ 3 Π u and B 3 Σ u - excited states. The total absorption cross-sections are computed to estimate isotope-fractionation constants, e , for four most common isotopologues: 32 S 32 S , 32 S 33 S , 32 S 34 S , and 32 S 36 S by quantum close-coupling (R-matrix) expansion approach and they are found to lie in a mostly opaque to competing absorbers spectral window. We suggest that the photochemistry and isotopic effects of S2 are of significant importance and provide data showing high sensitivity of mass-independent fractionation to excitation wavelength. Zero-point energy based constants e ZPE are estimated as well to compare with the obtained isotope effects and two modes for MIF are present in three-isotope plots; large isotopic effects were observed for both 36 S and 33 S with an excitation wavelength-dependent fluctuation. |
| Databáze: | OpenAIRE |
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