Ionization potentials and donor properties of nucleic acid bases and related compounds

Hush, Noel S.; Cheung, Agnes S.

doi:10.1016/0009-2614(75)80190-4

Cited by 329 publications

(191 citation statements)

References 22 publications

Supporting

Mentioning

160

Contrasting

Unclassified

Order By: Relevance

“…A slightly higher value of the lowest VIE (8.94 eV) was reported in an earlier PES study. 10 Although the tautomer ratio of C1, C2a, C2b and C3a in the PES study (463K) is expected to be 0.22:0.17:0.38:0.24 (as estimated 9 by the authors using ab initio thermodynamical data from Ref. 19 ), Trofimov et.…”

Section: Introductionmentioning

confidence: 95%

“…Previous ionization studies of cytosine consist of photoionization mass spectrometry (PIMS) measurements of AIEs, 6,7 photoelectron spectroscopy (PES) at the valence [8][9][10][11] and core level, 12 resonance enhanced multiphoton ionization (REMPI) experiments 13,14 and a number of electronic structure calculations. 9,[15][16][17][18] Trofimov et al 9 measured a valence-shell PES of cytosine.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

Kostko

Bravaya

Krylov

et al. 2010

Phys. Chem. Chem. Phys.

124

View full text Add to dashboard Cite

Photoionization of the cytosine dimer 2 SummaryWe report a combined theoretical and experimental study of ionization of cytosine monomers and dimers.Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60±0.05 eV and 7.6±0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra, suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the CH + signal at 9.20±0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH + appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.3

show abstract

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

Kostko

Bravaya

Krylov

et al. 2010

Phys. Chem. Chem. Phys.

124

View full text Add to dashboard Cite

show abstract

“…The orbital overlapping and the distribution of the HOMOs over the oligomer structure directly influence the charge distribution in the DNA molecule and the inner- [22] b Experimental data [22,26,27] sphere reorganization energy, respectively. We have calculated the inner-sphere reorganization energy and the vIP for the separated nucleobases and their pairs.…”

Section: B Inner-sphere Reorganization Energymentioning

confidence: 99%

Energetics of the hole transfer in DNA duplex oligomers

Berashevich

Chakraborty

2007

Chemical Physics Letters

View full text Add to dashboard Cite

We report on our calculations of the inner-sphere reorganization energy and the interaction of the π orbitals within DNA oligomers. The exponential decrease of the electronic coupling between the highest and second highest occupied base orbitals of the intrastrand nucleobases in the (A-T)n and (G-C)n oligomers have been found with an increase of the sequence number n in the DNA structure. We conclude that for realistic estimation of the electronic coupling values between the nucleobases within the DNA molecule, a DNA chain containing at least four base pairs is required. We estimate the geometry relaxation of the base pairs within the (A-T)n and (G-C)n oligomers (n = 1 − 6) due to their oxidation. The decrease of the inner-sphere reorganization energy with elongation of the oligomer structure participating in the oxidation process have been observed. The maximum degree of geometry relaxation of the nucleobase structures and correspondingly the higher charge density in the oxidized state are found to be located close to the oligomer center.

show abstract

“…Being of primary biological importance, ionized states of the DNA bases have been investigated both theoretically [14][15][16][17][18][19][20][21][22][23] and experimentally [14][15][16][24][25][26][27][28][29][30][31]; however, some questions are still unresolved. For example, the assignment of the bands in photoelectron spectra (PES) as corresponding to π or σ like states of the cations is still controversial.…”

Section: Introductionmentioning

confidence: 99%

Electronic Structure and Spectroscopy of Nucleic Acid Bases: Ionization Energies, Ionization-Induced Structural Changes, and Photoelectron Spectra

et al. 2010

View full text Add to dashboard Cite

We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed us-

show abstract

Ionization potentials and donor properties of nucleic acid bases and related compounds

Cited by 329 publications

References 22 publications

Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

Energetics of the hole transfer in DNA duplex oligomers

Electronic Structure and Spectroscopy of Nucleic Acid Bases: Ionization Energies, Ionization-Induced Structural Changes, and Photoelectron Spectra

Contact Info

Product

Resources

About