學術產出-Periodical Articles
Article View/Open
Publication Export
-
題名 Significant role of the DNA backbone in mediating the transition origin of electronic excitations of B-DNA - implication from long range corrected TDDFT and quantified NTO analysis 作者 郭光宇
Jian-Hao, L
Chai, Jeng-Da
Guo, Guang-Yu
Hayashi, Michitoshi貢獻者 應物所 日期 2012-07 上傳時間 18-Apr-2018 14:34:24 (UTC+8) 摘要 We systematically investigate the possible complex transition origin of electronic excitations of giant molecular systems by using the recently proposed QNTO analysis [J.-H. Li, J.-D. Chai, G. Y. Guo and M. Hayashi, Chem. Phys. Lett., 2011, 514, 362.] combined with long-range corrected TDDFT calculations. Thymine (Thy) related excitations of a B-DNA biomolecule are then studied as examples, where the model systems have been constructed by extracting from the perfect or an X-ray crystal (PDB code 3BSE) B-DNA structure with at least one Thy included. In the first part, we consider the systems composed of a core molecular segment (e.g. Thy, or di-Thy) and a surrounding physical/chemical environment of interest (e.g. backbone, adjacent stacking nucleobases) in gas phase and examine how the excitation properties of the core vary in response to the environment. We find that the orbitals contributed by the DNA backbone and surrounding nucleobases often participate in a transition of Thy-related excitations affecting their composition, absorption energy, and oscillator strength. A vast number of strongly backbone-orbital involved excitations are also found at an absorption wavelength below ∼180 nm predicted by TD-ωB97X. In the second part, we take into account geometrically induced variation of the excitation properties of various B-DNA segments, e.g. di-Thy, dTpdT etc., obtained from different sources (ideal and 3BSE). It is found that the transition origin of several Thy-related excitations of these segments is sensitive to slight conformational variations, suggesting that DNA with thermal motions may from time to time exhibit very different photo-induced physical and/or chemical processes. 關聯 Physical Chemistry Chemical Physics, 14(25):9092-103 資料類型 article DOI https://doi.org/10.1039/c2cp23676a dc.contributor 應物所 zh_Tw dc.creator (作者) 郭光宇 zh_TW dc.creator (作者) Jian-Hao, L en_US dc.creator (作者) Chai, Jeng-Da en_US dc.creator (作者) Guo, Guang-Yu en_US dc.creator (作者) Hayashi, Michitoshi en_US dc.date (日期) 2012-07 dc.date.accessioned 18-Apr-2018 14:34:24 (UTC+8) - dc.date.available 18-Apr-2018 14:34:24 (UTC+8) - dc.date.issued (上傳時間) 18-Apr-2018 14:34:24 (UTC+8) - dc.identifier.uri (URI) http://nccur.lib.nccu.edu.tw/handle/140.119/116894 - dc.description.abstract (摘要) We systematically investigate the possible complex transition origin of electronic excitations of giant molecular systems by using the recently proposed QNTO analysis [J.-H. Li, J.-D. Chai, G. Y. Guo and M. Hayashi, Chem. Phys. Lett., 2011, 514, 362.] combined with long-range corrected TDDFT calculations. Thymine (Thy) related excitations of a B-DNA biomolecule are then studied as examples, where the model systems have been constructed by extracting from the perfect or an X-ray crystal (PDB code 3BSE) B-DNA structure with at least one Thy included. In the first part, we consider the systems composed of a core molecular segment (e.g. Thy, or di-Thy) and a surrounding physical/chemical environment of interest (e.g. backbone, adjacent stacking nucleobases) in gas phase and examine how the excitation properties of the core vary in response to the environment. We find that the orbitals contributed by the DNA backbone and surrounding nucleobases often participate in a transition of Thy-related excitations affecting their composition, absorption energy, and oscillator strength. A vast number of strongly backbone-orbital involved excitations are also found at an absorption wavelength below ∼180 nm predicted by TD-ωB97X. In the second part, we take into account geometrically induced variation of the excitation properties of various B-DNA segments, e.g. di-Thy, dTpdT etc., obtained from different sources (ideal and 3BSE). It is found that the transition origin of several Thy-related excitations of these segments is sensitive to slight conformational variations, suggesting that DNA with thermal motions may from time to time exhibit very different photo-induced physical and/or chemical processes. en_US dc.format.extent 108 bytes - dc.format.mimetype text/html - dc.relation (關聯) Physical Chemistry Chemical Physics, 14(25):9092-103 dc.title (題名) Significant role of the DNA backbone in mediating the transition origin of electronic excitations of B-DNA - implication from long range corrected TDDFT and quantified NTO analysis en_US dc.type (資料類型) article dc.identifier.doi (DOI) 10.1039/c2cp23676a dc.doi.uri (DOI) https://doi.org/10.1039/c2cp23676a
