Ionization potentials and electron-donor ability of nucleic acid babes and their analogues

Орлов, В. М.; Смирнов, А. Н.; Varshavsky, Ya.M.

doi:10.1016/0040-4039(76)80120-7

Cited by 226 publications

(206 citation statements)

References 5 publications

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“…In contrast, a very recent core-level PES study 12 of cytosine suggested that 3 tautomers of cytosine are populated upon thermal vaporization at 450 K, with tautomer C2(a+b) (≈ 60 %) being the dominant species based on free energy calculations of Trygubenko et al 20 and Fogarasi. 19 A previous PIMS measurement from our group determined the AIE of cytosine monomer to be 8.65 (±0.05) eV, 6 in agreement with 8.68 eV reported in early PIMS work, 7 and within the range (8-9 eV) obtained using one and two color resonant 2 photon ionization spectroscopy by Nir et al 14 The latter work also reported that two tautomers, one keto (C1) and one enol (C2b), are prevalent in their laser desorption jet-cooled molecular beam.…”

Section: Introductionsupporting

confidence: 88%

“…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%

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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

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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

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Section: Introductionsupporting

confidence: 88%

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

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“…[21]. These results show that the DFT theory predicts the magnitude of the innersphere reorganization energy with a minimum error when compared to the experimental data [22,26,27]. Furthermore, we have also tested the application of the HF method and the DFT theory for the vertical ionization potential (vIP) calculations and have found significant qualitative and quantitative disagreement of the HF with the experimental data [22], while the Becke3P86 approximation is appropriate for this purpose.…”

Section: Methods Of Computationmentioning

confidence: 88%

“…From Table II it is clear that our calculation and the experimental results for the nucleobases are in good agreement except for cytosine. Unfortunately, the experimental values were defined as the difference between the vertical ionization potential and the adiabatic ionization potential, with values extracted from different sources [22,26,27]. As a result, in general the final values can be inaccurate due to the use of different experimental techniques and agreement of the theoretical data with the experiment is not completely reliable.…”

Section: B Inner-sphere Reorganization Energymentioning

confidence: 99%

“…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%

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Energetics of the hole transfer in DNA duplex oligomers

Berashevich

Chakraborty

2007

Chemical Physics Letters

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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.

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

2000

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Ionization potentials and electron-donor ability of nucleic acid babes and their analogues

Cited by 226 publications

References 5 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

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

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