Tautomery and H-bonding characteristics of 2-aminopurine: a combined experimental and theoretical study

An experimental and theoretical RHF, MP2 and DFT/6-31++G^** study is described of the matrix FT-IR spectra of monomer 2-aminopurine and H-bonded complexes of 2-aminopurine with water. 2-aminopurine occurs in Ar predominantly as the amino-N9H tautomer, but small amounts of the amino-N7H tautomer are also present. An approximate K_T value for this tautomeric equilibrium is found to be 0.016 (RHF) and 0.015 (DFT) using the infrared intensity measurement. Four H-bonded complexes of the abundant amino-N9H form with water are detected in the experimental FT-IR spectrum by their characteristic predicted absorptions, i.e. the three closed complexes N3 ^... H-O ^... H-N9, N1 ^... H-O ^... H-NH, N3 ^... H-O ^... H-NH and the open complex N7 ^... H-OH. From the experimental results, the proton affinity of the N7 atom in 2-aminopurine can be estimated. The dependence of the H-bond strength on the H-bond linearity is demonstrated by a correlation between the N ^... H distance and the N ^... H-O angle in closed N ^... H-O ^... H-N complexes. Received 10 December 2001 Published online 13 September 2002     

Electronic excitation and singlet-triplet coupling in uracil tautomers and uracil-water complexes

Electronic spectra of uracil in its diketo (lactam) form and five enol (lactim) tautomeric forms have been investigated by means of combined density functional and configuration interaction methods. We have simulated the effects of hydrogen bonding with a protic solvent by recomputing the spectrum of uracil in the presence of two, four, or six water molecules. Geometries of the electronic ground state and several low-lying excited states have been optimized. Spin-orbit coupling has been determined for correlated wavefunctions employing a non-empirical spin-orbit mean-field approach. In accord with experiment, we find the diketo tautomer to be the most stable one. The calculations confirm that the first absorption band arises from the ¹( π↦π^*) S ₀↦S ₂ excitation. The experimentally observed vibrational structure in this band originates from a breathing mode of the six ring. Complexation with water molecules is seen to cause a significant blue shift of n↦π^* excitations while leaving π↦π^* excitations nearly uninfluenced. Computed radiative lifetimes are presented for the experimentally known weak phosphorescence from the π↦π^* excited T₁ state. Among the uracil lactim tautomers, one is particularly interesting from a spectroscopic point of view. In this tautomer, the π↦π^* excitation gives rise to the S₁ state. Received 18 February 2002 / Received in final form 5 June 2002 Published online 13 September 2002     

Experimental transition probabilities in N III,N IV and N V spectra

We have obtained transition probabilities (Einstein's A values) of thirteen transitions in doubly (N III), six in triply (N IV) and two in four times (N V) ionized nitrogen spectra belonging to the 3s-3p and 3p-3d transitions using a relative line intensity ratio (RLIR) technique. The linear low-pressure pulsed arc was used as an optically thin plasma source operated at 51 400 K electron temperature and 2.2×10²³ m^-3 electron density in nitrogen plasma. Our A values are compared to recent theoretical and experimental data. Received 18 December 2001 / Received in final form 29 January 2002 Published online 28 June 2002     

Inelastic interactions of protons and electrons with biologically relevant molecules

Ionization and fragmentation of water and uracil molecules was studied both by electron and proton impact. A special coincidence technique allows on an event by event basis the investigation of product ions formed upon the collision of protons with neutral molecules including the identification of the charge state of the projectile. This enables the characterization of the ionization processes occurring, i.e. direct ionization, single electron capture or double electron capture for 0, 1 or 2 electrons that are transferred from the target to the projectile, respectively. For uracil the fragmentation patterns obtained by electron and proton impact ionization reveal close similarities and indicate a comparable amount of excitation for the two different ionization mechanisms at high enough projectile energies. Received 25 February 2002 Published online 13 September 2002     

Intracluster electron transfer from a metal atom/cluster followed by anionic oligomerization of vinyl molecules

Intracluster electron transfer and oligomerization reaction were investigated by mass spectrometry of clusters of alkali metal atom (M) with acrylonitrile (AN; CH₂=CHCN). In the photoionization mass spectra of M(AN)_n, magic numbers were clearly observed at n = 3k (k = 1-4 for M = Na and K, k = 1 for M = Li). The results of photodissociation of neutral K(AN)_n indicate that the n = 3 cluster has an anomalous stability relative to other sizes of clusters. The C=C bond in vinyl molecules is also found to be necessary to form the magic numbers by measuring the photoionization mass spectrum of K atom with propionitrile. These results strongly support the intracluster anionic oligomerization reaction initiated by electron transfer from the alkali atom. The quantum chemical calculations have revealed that the evaporation induced by excess energy generated by intracluster oligomerization is important to form the magic numbers in the present clusters. Received 29 November 2000     

From direct to absolute mass measurements: A study of the accuracy of ISOLTRAP

For a detailed study of the accuracy of the Penning trap mass spectrometer ISOLTRAP all expected sources of uncertainty were investigated with respect to their contributions to the uncertainty of the final result. In the course of these investigations, cross-reference measurements with singly charged carbon clusters ¹²C⁺ _n were carried out. The carbon cluster ions were produced by use of laser-induced desorption, fragmentation, and ionization of C₆₀ fullerenes and injected into and stored in the Penning trap system. The comparison of the cyclotron frequencies of different carbon clusters has provided detailed insight into the residual systematic uncertainty of ISOLTRAP and yielded a value of 8×10^-9. This also represents the current limit of mass accuracy of the apparatus. Since the unified atomic mass unit is defined as 1/12 of the mass of the ¹²C atom, it will be possible to carry out absolute mass measurements with ISOLTRAP in the future. Received 7 June 2002 Published online 6 November 2002 RID="a" ID="a"e-mail: a.kellerbauer@cern.ch RID="b" ID="b"Current address: Centre de Physique des Particules de Marseille, 13288 Marseille Cedex 9, France.     

K<Superscript>+</Superscript> production in proton-nucleus reactions and the role of momentum-dependent potentials

The production of K⁺-mesons in proton-nucleus collisions from 1.0 to 2.5GeV is analyzed with respect to one-step nucleon-nucleon ( NN → NYK ⁺) and two-step Δ-nucleon ( ΔN → K ⁺ YN) or pion-nucleon ( πN → K ⁺ Y) production channels on the basis of a coupled-channel transport approach (CBUU) including the kaon final-state interactions. The influence of momentum-dependent potentials for the nucleon, hyperon and kaon in the final state are studied as well as the importance of K⁺ elastic rescattering in the target nucleus. The transport calculations are compared to the experimental K⁺ spectra taken at LBL Berkeley, SATURNE, CELSIUS, GSI and COSY-Jülich. It is found that the momentum-dependent baryon potentials affect the excitation function of the K⁺ cross-section; at low bombarding energies of ∼ 1.0GeV the attractive baryon potentials in the final state lead to a relative enhancement of the kaon yield, whereas the net repulsive potential at bombarding energies ∼ 2GeV causes a decrease of the K⁺ cross-section. Furthermore, it is pointed out that especially the K⁺ spectra at low momenta (or kinetic energy T _K) allow to determine the in-medium K⁺ potential almost model independently due to a relative shift of the K⁺ spectra in kinetic energy that arises from the acceleration of the kaons when propagating out of the nuclear medium to free space, i.e. converting the potential energy to the kinetic energy of the free kaon. Received: 28 January 2002 / Accepted: 3 June 2002 / Published online: 19 November 2002 RID="a" ID="a"e-mail: Wolfgang.Cassing@theo.physik.uni-giessen.de Communicated by P. Schuck     

Structures of amide-water neutral complexes from dipole-bound anion formation

Using Rydberg Electron Transfer Spectroscopy, formation of dipole-bound anion complexes of formamide, N-methylformamide, N,N-dimethylformamide and N-methylacetamide with water has been studied. Each neutral complex can exist with several configurations and the lowest energy structures have been identified through comparison between Density Functional Theory calculations of the neutrals and measured electron binding energies of the observed weakly-bound anions. Received 13 March 2002 Published online 13 September 2002     

Low energy electron attachment to formic acid

Using a high resolution electron energy monochromator low energy electron attachment to formic acid is studied for the first time by means of mass spectrometric detection of the product anions. The largest dissociative electron attachment (DA) cross-section produces HCOO ^-+H with weaker channels for OH^- and O^- becoming apparent at higher incident energies. Received 23 January 2002 and Received in final form 9 February 2002 Published online 13 September 2002     

Modeling of recognition sites of nucleic acid bases aaand amide side chains of amino acids. Combination of experimental and theoretical approaches

A combined experimental-theoretical approach to modeling of building blocks of recognition complexes formed by nucleic acid bases and the amino-acids side-chain amino group is reviewed. The approach includes the temperature dependent field-ionization mass spectrometry and ab initio quantum chemical calculations. The mass spectrometric technique allows determination of interaction enthalpies of biomolecules in the gas phase, and the results it produces are directly comparable to the results obtained through theoretical modeling. In our works we have analyzed both thermodynamic and structural aspects of the recognition complexes of four canonical nucleic acid bases and acrylamide, which models the side chain of asparagine and glutamine. It has been shown that all bases can interact with amide group of the amino acids via their Watson-Crick sites when being incorporated into a single strand DNA or RNA. Stability of the complexes studied, expressed as - ΔH (kJ mole^-1) decreases as: m⁹Gua (- 59.5) > m ¹Cyt (- 57.0) > m ⁹Ade (- 52.0) ≫m ¹Ura (- 40.6). We have determined that in the double stranded DNA only purine bases can be recognized. Received 5 February 2002 and Received in final form 14 March 2002 Published online 13 September 2002     

In-beam spectroscopy of 253, 254No

In-beam conversion electron spectroscopy experiments have been performed on the transfermium nuclei ^{253, 254}No using the conversion electron spectrometer SACRED in nearly collinear geometry in conjunction with the gas-filled separator RITU at the University of Jyv?skyl?. The experimental setup is discussed and the spectra are compared to Monte Carlo simulations. The implications for the ground-state configuration of ²⁵³No are discussed. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: rdh@ns.ph.liv.ac.uk RID="b" ID="b"Present address: GANIL, F-14021 Caen, France. RID="c" ID="c"Permanent address: IReS Strasbourg, IN2P3-CNRS, F-67037-Strasbourg, France. RID="d" ID="d"Present address: CEA/DIF DCRE/SDE/LDN F-91680 Bruyeres-le-Chatel. RID="e" ID="e"Present address: Daresbury Laboratory, Daresbury WA4 4AD, UK. RID="f" ID="f"Permanent address: IPN Lyon, IN2P3-CNRS, F-69037 Lyon, France.     

Phase transition and random-field induced domain wall response of SrTi O 3

The dielectric permittivity ε^′ - i of SrTi ¹⁸O ₃ (STO18) is studied under a dc electric field E as a function of the temperature, T. In ε^′ vs. T, a double-peak is found when 0 < E < 30 KV/m. While the peak at high-T is attributed to the smeared ferroelectric phase transition, the low-T one is induced by domain wall motion. The transverse Ising model including an external homogeneous and quenched random-fields is successfully used to describe both the smeared phase transition and the domain wall response in the low-T domain state. The calculations are in good agreement with the experimental results. Received 4 January 2002 / Received in final form 25 March 2002 Published online 19 July 2002     

Interaction between aromatic amine cations and nonpolar solvents: Infrared spectra of isomeric aniline -Ar n ( ) complexes

Infrared (IR) photodissociation spectra of the aniline⁺-Ar_n cations, An ⁺ - Ar _n (n = 1, 2), are analyzed in the vicinity of the N-H stretch fundamentals. The complexes are produced in an electron impact (EI) ion source which produces predominantly the most stable cluster isomers. Two isomers of An⁺-Ar are identified by their characteristic N-H stretch frequencies: the planar proton-bound global minimum, in which the Ar ligand forms a nearly linear H-bond to the amino group, and the less stable π-bound local minimum, in which the Ar atom is attached to the π-electron system of the aromatic ring. This result is the first unambiguous detection of the most stable H-bound An⁺-Ar dimer. All previous spectroscopic studies of An⁺-Ar employed resonance enhanced multiphoton ionization (REMPI) of neutral An-Ar and identified only the less stable π-bound cation due to restrictions arising from the Franck-Condon principle. The EI-IR spectrum of An⁺-Ar₂ shows that the most stable structure of this trimer features two equivalent H-bonds (C_2v symmetry). The interpretation of the experimental data is supported by quantum chemical calculations. The ab initio potential of An⁺-Ar calculated at the UMP2/6-311G(2df, 2pd) level features H-bound global minima ( D _e = 513 cm^-1) and π-bound local minima ( D _e = 454 cm^-1), with a barrier of V _b ≈ 140 cm^-1 for isomerization from the π-bound toward the H-bound minimum. Received 4 February 2002 Published online 13 September 2002     

Fluctuation-induced magnetotransport of superconductors in the quasiballistic regime

We study the fluctuation-induced magnetotransport of a two-dimensional superconductor in the quasiballistic regime, where ξ _GL(T) ≪ ℓ (ℓ is the electron mean free path and ξ _GL(T) is the Ginzburg-Landau coherence length). The magnetoconductivity is evaluated in the nonlocal fluctuation regime thereby extending the existing theory valid in the local limit. We show that the Maki-Thompson (MT) and density-of-states (DOS) contributions strongly compensate each other and their sum is negligible in comparison with the Aslamazov-Larkin (AL) term. The hierarchy of the fluctuation contributions to the magnetoconductivity in the high-field limit is also qualitatively discussed. Received 10 July 2002 / Received in final form 21 November 2002 Published online 7 May 2003     

Charge radius change in the heavy tin isotopes until A = 132 from laser spectroscopy

Laser spectroscopy measurements have been carried out on the very neutron-rich tin isotopes with the COMPLIS experimental setup. Using the 5s ²5p ²³ P ₀ → 5s ²5p6s ³ P ₁ optical transition, hyperfine spectra of ^126-132Sn and ^{125m, 127m, 129m-131m}Sn where recorded for the first time. The variation of the mean-square charge radius ( δ〈r ²〉) between these nuclei and nuclear moments of the isomers and the odd isotopes were thus measured. An odd-even staggering which inverts at A = 130 is clearly observed. This indicates a small appearance of a plateau on the δ〈r ²〉 which has to be confirmed by measuring the isotope shift beyond A = 132. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: leblanc@ipno.in2p3.fr     

Candidates for chiral doublet bands in 136Nd

The even-even nucleus ¹³⁶Nd was studied via in-beam γ-ray spectroscopy using the ¹⁶O + ¹²⁵Te reaction at 100 MeV and the EUROBALL array. One new dipole band was observed. Together with a previously identified dipole band, whose position in the level scheme is revised, the new band forms a doublet structure similar to the recently observed chiral bands in the odd-odd neighboring nuclei. This would be the first case of a chiral doublet in an even-even nucleus. Received: 23 May 2002 / Accepted: 30 September 2002 / Published online: 27 November 2002 RID="a" ID="a"e-mail: costel.petrache@unicam.it RID="b" ID="b"Present address: Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. RID="c" ID="c"Present address: Gesellschaft für Schwerionenforschung D-64291 Darmstadt, Germany. Communicated by C. Signorini     

Electronic structure and metal-insulator transition in SrTi 1 - x Ru xO 3

We studied the changes in the electronic structure of SrTi_1-xRu_xO₃ across the metal-insulator transition. The parent compound, SrTiO₃, is a well known diamagnetic insulator; whereas the doped compound, SrTi_1-xRu_xO₃, becomes a ferromagnetic metal above x _C = 0.35. The techniques used in the study were photoemission (PES) and O 1 s X-ray absorption (XAS) spectroscopy. The experimental spectra were analyzed in terms of band structure and Hubbard model calculations. The PES and XAS spectra of SrTi_1-xRu_xO₃ show the Ru 4 d bands growing in the band gap of SrTiO₃ . The analysis in terms of the Hubbard model indicates that the Ti 3 d and Ru 4 d bands are mostly decoupled. This suggests that the metal-insulator transition is a percolation transition like that of metals embedded in a rare gas matrix. Electron correlation effects are present in this system, but they do not seem to play a major role in the transition. Received 10 September 2001     

The measurement of the electronic g-factor in hydrogen-like ions --A promising tool for determining fundamental and nuclear constants

We describe a double-Penning-trap experiment suitable for testing QED in strong fields by determining the electronic g-factor of a single hydrogen-like ion in its ground state. Our measurements on ¹²C^{5 +} reach a relative accuracy of 2×10^-9, where the largest uncertainty results from the mass of the electron. Together with equally precise theoretical predictions therefore, it is possible to evaluate a new value for the electron's mass. The possibilities to obtain other fundamental constants and nuclear parameters are lined out. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: t.beier@gsi.de     

Solvation and chemical reaction of sodium in water clusters

Na_m(H₂O)_n Clusters ( n = 1...200, m = 1...50) are formed in a recently build pick-up arrangement. Preformed water clusters traverse a sodium oven, where sodium atoms are picked up. At low sodium vapour pressure ( < 1×10^-4 mbar) pure Na(H₂O)_n clusters are observed in the mass spectra. At high sodium vapour pressure ( > 1×10^-3 mbar) the water cluster pick up more than 50 Na atoms and reaction products Na(NaOH)_n ( n = 2, 4...50) dominate the mass spectra. The even number of NaOH units in the products indicate that also in a finite cluster the reaction occurs in pairs as in the macroscopic reaction. Received 4 December 2000     

Conversion electron measurement in the β<Superscript>-</Superscript>-decay of <Superscript>151</Superscript>Pr

The β^--decay of ¹⁵¹Pr produced by the thermal neutron-induced fission of ²³⁵U has been studied using an on-line isotope separator. From an internal-conversion electron measurement with a Si(Li) detector, K-conversion coefficients were obtained for 20 γ-transitions. Spins and parities of 6 excited levels in ¹⁵¹Nd were newly determined from the deduced multipolarities: even parities for the 543 and 627 keV levels, odd parities for 250 and 599 keV, (3/2, 5/2)⁺ for 685 keV, and (1/2, 3/2)⁺ for 880 keV. The level structure was compared with the rotation-vibration coupling Nilsson model. Received: 28 June 2002 / Accepted: 31 October 2002 / Published online: 25 February 2003 RID="a" ID="a"e-mail: ykojima@hiroshima-u.ac.jp Communicated by J. ?yst?