Citation: YUAN Shuai, MA Jing, ZHANG Wen-Ying, SHU Kun-Xian, DOU Yu-Sheng. Semiclassical Dynamics Simulation and CASSCF Calculation for 5-Methyl Cytosine and Cytosine[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201209284 shu

Semiclassical Dynamics Simulation and CASSCF Calculation for 5-Methyl Cytosine and Cytosine

1.
Institute of Bioinformatics, Chongqing University of Posts and Telecommunications, Chongqing 400065, P. R. China

Received Date: 24 August 2012
Available Online: 28 September 2012
Fund Project: 国家自然科学基金(21073242) (21073242)重庆市自然科学基金(CSTC2011jjA00009, CSTC2009BB5419) (CSTC2011jjA00009, CSTC2009BB5419)重庆市教委科学技术项目(KJ120516)资助 (KJ120516)

We performed a semiclassical dynamics simulation study of the photophysical deactivation of 5m-cytosine (5m-Cyt) and cytosine (Cyt) induced by ultraviolet radiation of 267 nm. The results show that deactivation of the excited state of 5m-Cyt and Cyt results from the distortion of the C₅－C₆ bond and the out-of-plane vibration of methyl (or H₅) and the H6 atom. A so-called“biradical state”, in which the methyl (or H₅) and H₆ atoms are nearly perpendicular to the average ring plane and displaced in opposite directions, is formed at the decay point. The vibration frequency of the methyl derivative is less than that of the H atom derivative because of its increased volume relative to the H atom. The results indicated that molecular deformation at the C₅ atom of 5m-Cyt will be weakened and will result in a longer excited lifetime of 5m-Cyt. Complete active space self-consistent field (CASSCF) calculations show that the energy of the conical intersection (CI) of 5m-Cyt is 0.3 eV higher than that of Cyt. This suggests that promotion to the CI point for 5m-Cyt requires the molecule to overcome a larger energetic barrier, which results in a longer excited state lifetime than Cyt.
- 5-Methylcytosine,
- Cytosine,
- Semiclassical dynamic simulation,
- CASSCF,
- Lifetime of excited state
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