Theoretical determination of electron affinity and ionization potential of DNA and RNA bases

The ionization potentials and electron affinities of thymine, cytosine, adenine, guanine, and uracil were determined at density functional level using different exchange‐correlation functionals and basis sets. Results showed that the computed ionization potentials are very close to the experimental counterparts. The sign of adiabatic electron affinities of adenine, thymine, and uracil is unaffected by the used level of theory while that for guanine and cytosine depends on both the used potential and basis set. Vertical electron affinities are always negative in agreement with the experimental indications. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1243–1250, 2000

[1]  C. Desfrançois,et al.  Valence and Dipole Binding of Electrons to Uracil , 1998 .

[2]  M. Sevilla,et al.  Structure and Relative Stability of Deoxyribose Radicals in a Model DNA Backbone: Ab Initio Molecular Orbital Calculations , 1995 .

[3]  L. Adamowicz,et al.  Electron attachment to uracil. Theoretical ab initio study , 1993 .

[4]  R. J. Boyd,et al.  Effects of Ionizing Radiation on Crystalline Cytosine Monohydrate , 1998 .

[5]  J. V. Ortiz,et al.  Anionic and Neutral Complexes of Uracil and Water , 1999 .

[6]  E. Illenberger,et al.  Resonant dissociation of DNA bases by subionization electrons , 1998 .

[7]  Harel Weinstein,et al.  Mechanisms of nucleophilic addition to activated double bonds : 1,2- and 1,4-Michael addition of ammonia , 1993 .

[8]  Dennis R. Salahub,et al.  Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation , 1992 .

[9]  A. Becke.  A multicenter numerical integration scheme for polyatomic molecules , 1988 .

[10]  I. Gould,et al.  Accurate prediction of the solvation of nucleotide base pairs using an ab initio continuum model , 1994 .

[11]  D. Herschbach,et al.  Cluster Beam Chemistry: Hydration of Nucleic Acid Bases; Ionization Potentials of Hydrated Adenine and Thymine , 1996 .

[12]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[13]  M. Sevilla,et al.  Ab initio molecular orbital calculations of DNA radical ions. 5. Scaling of calculated electron affinities and ionization potentials to experimental values , 1995 .

[14]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[15]  K. Voit,et al.  Specific formation of electron gain and loss centres in X-irradiated oriented fibres of DNA at low temperatures. , 1984, Faraday discussions of the Chemical Society.

[16]  H. Abdoul-Carime,et al.  Electron attachment to isolated nucleic acid bases , 1996 .

[17]  R. J. Boyd,et al.  Comparison of Experimental and Calculated Hyperfine Coupling Constants. Which Radicals Are Formed in Irradiated Guanine , 1998 .

[18]  A. Gräslund,et al.  Ionic base radicals in -irradiated DNA. , 1971, Biochimica et biophysica acta.

[19]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[20]  N. Hush,et al.  Ionization potentials and donor properties of nucleic acid bases and related compounds , 1975 .

[21]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[22]  J. H. Hendricks,et al.  Dipole bound, nucleic acid base anions studied via negative ion photoelectron spectroscopy , 1996 .

[23]  K. Szczepaniak,et al.  Matrix isolation infrared studies of nucleic acid constituents: Part 4. Guanine and 9-methylguanine monomers and their keto—enol tautomerism☆ , 1987 .

[24]  Y. Yu,et al.  Intrinsic acidity and redox properties of the adenine radical cation 1 1 Dedicated to the memory of , 1999 .

[25]  M. Sevilla,et al.  Relative abundances of primary ion radicals in .gamma.-irradiated DNA: cytosine vs. thymine anions and guanine vs. adenine cations , 1991 .

[26]  R. Bartlett,et al.  Electron affinity of NH: a coupled-cluster and Hartree-Fock density-functional-theory study , 1997 .

[27]  E. Sagstuen,et al.  Radiation damage to DNA base pairs. II. Paramagnetic resonance studies of 1-methyluracil x 9-ethyladenine complex crystals X-irradiated at 10 K. , 1998, Radiation research.

[28]  Erich Wimmer,et al.  Density functional Gaussian‐type‐orbital approach to molecular geometries, vibrations, and reaction energies , 1992 .

[29]  Sukhodub Lf,et al.  Ionization potentials of nucleic acid nitrogenous bases , 1976 .

[30]  K. Kubulat,et al.  Matrix isolation infrared studies of nucleic acid constituents. 5. Experimental matrix-isolation and theoretical ab initio SCF molecular orbital studies of the infrared spectra of cytosine monomers , 1988 .

[31]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[32]  E. Sagstuen,et al.  Radiation damage to DNA base pairs. I. Electron paramagnetic resonance and electron nuclear double resonance study of single crystals of the complex 1-methylthymine.9-methyladenine X-irradiated at 10K. , 1996, Radiation research.

[33]  P. Wenthold.  A computational study of the electron affinity of silene , 1998 .

[34]  L. Grace,et al.  REMPI Spectroscopy of Jet-Cooled Guanine , 1999 .

[35]  Timothy Clark,et al.  Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–F , 1983 .

[36]  Y. Varshavsky,et al.  Ionization potentials and electron-donor ability of nucleic acid babes and their analogues , 1976 .

[37]  M. Sevilla,et al.  Ab initio molecular orbital calculations of DNA bases and their radical ions in various protonation states: evidence for proton transfer in GC base pair radical anions , 1992 .

[38]  R. J. Boyd,et al.  Radiation Products of Thymine, 1-Methylthymine, and Uracil Investigated by Density Functional Theory , 1998 .

[39]  Antoine Moreau,et al.  Cluster size effects upon anion solvation of N-heterocyclic molecules and nucleic acid bases , 2000 .

[40]  G. Gallup,et al.  ELECTRON ATTACHMENT ENERGIES OF THE DNA BASES , 1998 .

[41]  G. P. Ford,et al.  Theoretical study of gas-phase methylation and ethylation by diazonium ions and rationalization of some aspects of DNA reactivity , 1983 .

[42]  G. P. Ford,et al.  Prediction of nucleoside-carcinogen reactivity. Alkylation of adenine, cytosine, guanine, and thymine and their deoxynucleosides by alkanediazonium ions. , 1990, Chemical research in toxicology.

[43]  Daniel M. Neumark,et al.  Anion spectroscopy of uracil, thymine and the amino-oxo and amino-hydroxy tautomers of cytosine and their water clusters , 1998 .

[44]  R. Bartlett,et al.  A theoretical study of the valence‐ and dipole‐bound states of the nitromethane anion , 1996 .

[45]  W. Bernhard.  Sites of electron trapping in DNA as determined by ESR of one-electron-reduced oligonucleotides , 1989 .

[46]  A. Gräslund,et al.  Ionic Base Radicals in γ-irradiated Oriented Non-deuterated and Fully Deuterated DNA , 1975 .

[47]  L. Adamowicz,et al.  Theoretical ab initio calculations of the electron affinity of thymine , 1994 .