MENU ▼
Read by QxMD icon Read
search
OPEN IN READ APP
JOURNAL ARTICLE

Parameters for excess electron transfer in DNA. Estimation using unoccupied Kohn-Sham orbitals and TD DFT

Martín Félix, Alexander A Voityuk
Journal of Physical Chemistry. A 2008 September 25, 112 (38): 9043-9
18754606
We show that the energetics and electronic couplings for excess electron transfer (EET) can be accurately estimated by using unoccupied Kohn-Sham orbitals (UKSO) calculated for neutral pi stacks. To assess the performance of different DFT functionals, we use MS-PT2 results for seven pi stacks of nucleobases as reference data. The DFT calculations are carried out by using the local spin density approximation SVWN, two generalized gradient approximation functionals BP86 and BLYP, and two hybrid functionals B3LYP and BH&HLYP. Best estimations within the UKSO approach are obtained by the B3LYP and SVWN methods. TD DFT calculations provide less accurate values of the EET parameters as compared with the UKSO data. Also, the excess charge distribution in the radical anions is well described by the LUMOs of neutral systems. In contrast, spin-unrestricted DFT calculations of radical anions considerably overestimate delocalization of the excess electron. The excellent results obtained for the ground and excited states of the radical anions (excitation energy, transition dipole moment, electronic coupling, and excess electron distribution) by using UKSO of neutral dimers suggest an efficient strategy to calculate the EET parameters for DNA pi stacks.

Comments

You need to log in or sign up for an account to be able to comment.

No comments yet, be the first to post one!

Related Papers

Available on the App Store

Available on the Play Store
Remove bar
Read by QxMD icon Read
18754606
×

Search Tips

Use Boolean operators: AND/OR

diabetic AND foot
diabetes OR diabetic

Exclude a word using the 'minus' sign

Virchow -triad

Use Parentheses

water AND (cup OR glass)

Add an asterisk (*) at end of a word to include word stems

Neuro* will search for Neurology, Neuroscientist, Neurological, and so on

Use quotes to search for an exact phrase

"primary prevention of cancer"
(heart or cardiac or cardio*) AND arrest -"American Heart Association"