### MS-CASPT2 Studies on the Photophysics of Selenium-Substituted Guanine Nucleobase.

*Ontology highlight*

**ABSTRACT**: The MS-CASPT2 method has been employed to optimize minimum-energy structures of 6-selenoguanine (6SeGua) and related two- and three-state intersection structures in and between the lowest five electronic states, i.e., S2(1??*), S1(1 n?*), T2(3 n?*), T1(3??*), and S0. In combination with MS-CASPT2 calculated linearly interpolated internal coordinate paths, the photophysical mechanism of 6SeGua has been proposed. The initially populated S2(1??*) state decays to either S1(1 n?*) or T2(3 n?*) states through a three-state S2/S1/T2 intersection point. The large S2/T2 spin-orbit coupling of 435 cm-1, according to the classical El-Sayed rule, benefits the S2 ? T2 intersystem crossing process. The S1(1 n?*) state that stems from the S2 ? S1 internal conversion process at the S2/S1/T2 intersection point can further jump to the T2(3 n?*) state through the S1 ? T2 intersystem crossing process. This process does not comply with the El-Sayed rule, but it is still related to a comparatively large spin-orbit coupling of 39 cm-1 and is expected to occur relatively fast. Finally, the T2(3 n?*) state, which is populated from the above S2 ? T2 and S1 ? T2 intersystem crossing processes, decays to the T1(3??*) state via an internal conversion process. Because there is merely a small energy barrier of 0.11 eV separating the T1(3??*) minimum and an energetically allowed two-state T1/S0 intersection point, the T1(3??*) state still can decay to the S0 state quickly, which is also enhanced by a large T1/S0 spin-orbit coupling of 252 cm-1. Our proposed mechanism explains experimentally observed ultrafast intersystem crossing processes in 6SeGua and its 835-fold acceleration of the T1 state decay to the S0 state compared with 6tGua. Finally, we have found that the ground-state electronic structure of 6SeGua has more apparent multireference character.

**PROVIDER: **S-EPMC6649137 | BioStudies |

**REPOSITORIES: ** biostudies

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