Effect of guanine-cytosine base pair orientation and cluster size on ionization energy and charge distribution: A theoretical study

Density functional calculations with B3LYP/aug-cc-pVDZ level of theory suggest that the vertical ionization energy (VIE) is minimum for 0° orientation angle of guanine-cytosine (GC). _n (. n=. 2-6) base pairs, and maximum at around 30°, which is close to the natural base orientation angle (36°) in DNA. As the (GC). _n cluster size is increased, the VIE value is decreased substantially from n=. 1 to n=. 3 (7.23-5.76. eV) followed by a less dramatic decrease for larger n values. In each cationic (GC). _n cluster, the charge distribution among the G bases shows a pattern that depends upon odd or even number of base pairs in the cluster. At a very low temperature, when the orientation angle is frozen to its equilibrium value (around 36°), the CT rate is expected to drop significantly (large VIE value) in comparison with the rates at higher temperatures when small orientation angles are accessible with lower VIE values.