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     

On the mechanism of nonradiative decay of DNA bases: ab initio and TDDFT results for the excited states of 9H-adenine

Minimum-energy reaction paths and corresponding potential-energy profiles have been computed for the lowest excited states of the amino form of 9H-adenine. Complete-active- space self-consistent-field (CASSCF) and density functional theory (DFT) methods have been employed. The potential-energy function of the lowest ¹πσ^* state, nominally a 3s Rydberg state, is found to be dissociative with respect to the stretching of the NH bond length of the azine group. The ¹πσ^* potential-energy function intersects not only those of the ¹ππ^* and ¹ nπ^* excited states, but also that of the electronic ground state. The ¹ππ^*- ¹πσ^* and ¹πσ^*-S₀ intersections are converted into conical intersections when the out-of-plane motion of the active hydrogen atom is taken into account. It is argued that the predissociation of the ¹ππ^* and ¹ nπ^* states by the ¹πσ^* state and the conical intersection of the ¹πσ^* state with the S₀ state provide the mechanism for the ultrafast radiationless deactivation of the excited singlet states of adenine.     

Understanding the newly observed Y(4008) by Belle

Very recently a new enhancement around 4.05 GeV was observed by the Belle experiment. We discuss some possible assignments for this enhancement, i.e. the ψ(3S) and D^*D̄^* molecular states. In these two assignments, Y(4008) can decay into J/ψπ⁰π⁰ with a branching ratio comparable with that of Y(4008)→J/ψπ⁺π^-. Thus, one suggests high energy experimentalists to look for Y(4008) in J/ψπ⁰π⁰ channel. Furthermore one proposes further experiments to search for the missing channels DD̄, DD̄^*+h.c. and especially χ_cJπ⁺π^-π⁰ and η_cπ⁺π^-π⁰, which will be helpful to distinguish the ψ(3S) and D^*D̄^* molecular state assignments for this new enhancement. PACS 13.30.Eg 13.75.Lb     

Excitation of the Roper resonance in single- and double-pion production in nucleon-nucleon collisions⋆

In most investigations the Roper resonance is sensed only very indirectly via complex partial-wave analyses. We find indications for its excitation in the invariant nπ⁺ mass spectrum of the pp → npπ⁺ reaction at M ≈ 1360 MeV with a width of ≈ 150 MeV . The values fit very favorably to the most recent phase shift results as well as to the observations at BES. In the near-threshold two-pion production pp → ppπ⁰π⁰ , where the Roper excitation and its subsequent decays via the routes N ^* → Δπ → Nππ and N ^* → Nσ are the only dominant processes, we find its direct decay into the Nσ channel to be the by far dominating decay process --in favor of a monopole excitation of the Roper resonance.     

Study of N*(1440) from J/Ψ decays

For J/Ψ↦ pπ⁰ and pπ⁺π^-, the π⁰ p and pπ⁺π^- systems are limited to be pure isospin-(1/2) due to isospin conservation. This is a big advantage in studying N^* resonances from J/Ψ decays, compared with πN and γN experiments. The process J/Ψ↦ N ^* or p provides a new way to probe the internal structure of the N^* resonances. Here we report a quark model calculation for J/Ψ↦ p, N ^*(1440) and N ^*. The implication for the internal structure of N ^*(1440) is discussed. Received: 1 June 2001 / Accepted: 20 June 2001     

Construction of Fredholm representations and a modification of the Higson-Roe corona

The Fredholm representation theory is well adapted to the construction of homotopy invariants of non-simply-connected manifolds by means of the generalized Hirzebruch formula [σ(M)] = 〈L(M)ch _A f*ξ, [M]〉 ∈ K _A ⁰(pt) ⊗ Q, where A = C*[π] is the C*-algebra of the group π, π = π ₁(M). The bundle ξ ∈ K _A ⁰(Bπ) is the canonical A-bundle generated by the natural representation π → A. Recently, the first author constructed a natural family of Fredholm representations that lead to a symmetric vector bundle on the completion of the fundamental group with a modification of the Higson-Roe corona, provided that the completion is a closed manifold.     

ρ0-ω mixing in U(3)L×U(3)R chiral theory of mesons}

In this paper, U(3)_L×U(3)_R chiral theory of mesons is extended to the leading order in quark mass expansion in order to evaluate the ρ⁰-ω mixing. It is shown that the use of path integral method to integrate out the quark fields naturally leads to the ρ⁰-ω mixing vertices, and this mixing is entirely from the quark loop in this theory. The off-shell behaviour of the mixing amplitude is analyzed. The on-shell mixing amplitude is obtained from the decay ω→π⁺π⁻. Furthermore, the constraints on the light quark mass parameters are extracted from the ρ⁰-ω mixing and the mesons masses, and the mass splitting of K^*(892)-mesons is predicted. Received: 30 January 1998 / Revised version: 3 June 1998     

Luminescence of oxotetrahydrobenzo[c]phenanthridine in polar and nonpolar solvents: Inversion of the energy levels of the Sππ* and Tnπ* states

The spectral-luminescent properties and electronic-level structure of a derivative of oxotetrahydrobenzo[c]phenanthridine—3,3-dimethyl-1,2,3,4-tetrahydrobenzo[c]phenanthridine-1-one (DTP)—in polar and nonpolar solutions are studied by the luminescence and picosecond spectroscopy techniques at 293 and 77 K. It is shown that DTP exhibits ππp* fluorescence only in polar proton-containing methanol, ethanol, and n-propanol and that this fluorescence is associated with a chromophore + alcohol complex. Solutions of DTP in n-propanol and the nonpolar mixture methylcyclohexane + toluene (6:1) at 77 K display ππp* phosphorescence with a quantum yield Φ_Ph=0.1, a lifetime τ_Ph=1.9 s, and a frequency of the 0-0 transition equal to 21550 cm⁻¹. The fact that DTP fluorescence is absent in aprotic solvents and exists in alcohols is explained by the inversion of the energy levels of the S _ππ* and T _n π* states, as a result of which the energy level of the fluorescing S _ππ* state in alcohol becomes the lowest. The picosecond spectra and kinetics of the inducedS _n (ππ*) ← S ₁(π π*) and T _k (ππ*) ← T ₁(ππ*) absorption made it possible to estimate the lifetime of the S ₁(ππ*) state of DTP in n-propanol at 293 K (20±10 ps) and the position of the triplet-triplet absorption peak (495 nm). __________ Translated from Optika i Spektroskopiya, Vol. 94, No. 6, 2003, pp. 993–998. Original Russian Text Copyright ? 2003 by Bondarev, Knyukshto, Tikhomirov, Pyrko.     

Model of the photostimulated fragmentation of PETN molecules in selective photoinitiation

A model of the photostimulated fragmentation of the PETN molecule irradiated by the first harmonic of a neodymium laser (1060 nm) is proposed. Photoexcitation at 1060 nm leads to the n → π* transition of the 2p nonbinding electron of the oxygen to the π* antibonding orbital, a transition that causes the rupture of the O-N bond and the formation of NO₂^* radicals, thereby ensuring a further development of explosive decomposition. In the case of a free molecule or a molecule located on the surface of a microcrystal, the process does not require any thermal activation. In the case of a molecule at a regular lattice site, an additional activation energy (0.4 eV) is needed to overcome the potential barrier associated with the passage of through a bottleneck between the nearest-neighbor molecules.     

The K * Kπ and ρππ couplings in QCD

The light cone QCD sum rules are derived for the K ^* Kπ coupling g _K ^* Kπ and the ρππ coupling g _ρππ. The contribution from the excited states and the continuum is subtracted cleanly through the double Borel transform with respect to the two external momenta, p ₁ ², p ₂ ²= (p−q)². Our result g _K ^* Kπ= (8.7 ± 0.5) and g _ρππ= (11.5 ± 0.8) is in good agreement with the experimental value. Received: 31 July 1998 / Revised version: 20 November 1998     

Luminescence efficiency of aromatic carboxylates of europium and terbium when methylene bridges and nitro groups are present in the ligands

We discuss the possibility of optimizing the brightness of luminescence for phenylcarboxylates, naphthylcarboxylates, and indolylcarboxylates of europium and terbium and their adducts with 1,10-phenanthroline and 2,2′-bipyridine by modifying the ligands. We have studied the efficiency of luminescence and luminescence excitation. We consider the effect of blocking energy transfer from the ligands to the Eu³⁺ and Tb³⁺ ions by methylene (-CH₂-) bridges dividing the π-electron system of the ligands into two parts and by the electronacceptor nitro group (-NO₂). We have analyzed the pathways for transfer and degradation of the excitation energy at 77 K and 300 K. From the phosphorescence spectra of gadolinium salts, we have determined the energies of the lowest excited triplet states of the ligands. We consider the effect of the relative positions of the triplet levels of the ligands and the excited levels of the Eu³⁺ and Tb³⁺ ions on the luminescence efficiency. We found channels for dissipation of the excitation energy via the ππ* and nπ* states of the aromatic system of the carboxylate and the NO₂ group. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 48–54, January–February, 2007.     

The search for and study of the strange multibaryon states in systems with Λ-hyperon and Ks0 -meson in pA collision at momentum of 10 GeV/c

Exotic strange multibaryon states have been observed in the effective mass spectra of: Λπ^±, Λπ⁺π⁻, Λp, Λpp, Λπp, ΛΛ and ΛK _s ⁰, K _s ⁰ p, K _s ⁰π^± subsystems. The measured Λ/π⁺ ratio for average multiplicities from the pC reaction is equal to (5.3 ± 0.8) × 10⁻², and it is approximately two times larger than the Λ/π⁺ ratio simulated by the FRITIOF model and than that of experimental pp reactions at the same energy. The observed wellknown resonances Σ*⁺ (1385) and K*^± (892) from PDG are good tests of this method. The mean value of the mass for the Σ*⁻(1385) resonance is shifted to 1370 MeV/c ² and the width is two times larger than the same value from PDG. Such kind of behavior for the width and invariant mass of Σ*⁻ (1385) resonance is interpreted as an extensive contribution from stopped Ξ⁻ → Λπ⁻ and medium effect. There is enhancement of the production contribution for all observed hyperons. A few events were registered by hypothesis of light H ⁰ and heavy H ^{0, +} dihyperons. Dihyperons were observed by weak decay channels: (Σ⁻ p), (Λpπ⁻), (Λpπ⁰), and (K ⁻ pp). The text was submitted by the author in English.     

Λc(2940)+: a possible molecular state?

A new baryonic state Λ_c(2940)⁺ has recently been discovered by the Babar collaboration in the D⁰p channel. Later Belle collaboration also observed this state in the Σ_c(2455)^0,++π^±→Λ_c ⁺π⁺π^- channel. The mass of Λ_c(2940)⁺ is just a few MeV below the sum of D^*0 and p masses suggesting a possibility that this state may be a D^*0p molecular state. In this paper we study whether such a molecular state can be consistent with data. We find that the molecular structure can explain data and that if Λ_c(2940)⁺ is a D^*0p molecular state it is likely a 1/2^- state. Several other decays modes are also suggested to further test the molecular structure of Λ_c ⁺(2940). PACS 13.30.Eg; 14.20.Lg; 12.39.Pn     

Collision-energy-resolved Penning ionization electron spectroscopy of toluene and chlorotoluenes

Stereodynamics in ionization of toluene and o-, p-chlorotoluenes by collision with He^*(2³S) metastable atoms were investigated by two-dimensional collision-energy/electron-energy-resolved Penning ionization electron spectroscopy. Anisotropic interactions around the molecule were studied by the collision energy dependence of partial ionization cross-sections (CEDPICS) as well as model potential calculations, and shielding effect by the methyl group was observed in CEDPICS for ionization from Cl lone-pair orbitals of o- chlorotoluene. Attractive interaction with He^*(2³S) around the π orbital region was found to be larger for toluene rather than o-, p- chlorotoluenes. Exterior electron density (EED) calculation of partial ionization cross-sections in Penning ionization and negative CEDPICS for ionization band observed in ca. 4 eV in electron energy indicated that π^-2π⁺¹ shake-up state was observed in Penning ionization electron spectroscopy of toluene.     

The reaction np→ppπ- from threshold up to 570 MeV

Due to a coding error, the previous paper quoted incorrect values for the differential cross sections dσ/dM_pp and dσ/dΩ_π ^* of the process np→ppπ^-. The online version of the original article can be found at     

K0πand K*0Σ+ photoproduction off the proton

The exclusive reactions γp → K ^*0Σ⁺(1189) and γp → K ⁰π⁰Σ⁺(1189) , leading to the p 4π⁰ final state, have been measured with a tagged photon beam for incident energies from threshold up to 2.5GeV. The experiment has been performed at the tagged photon facility of the ELSA accelerator (Bonn). The Crystal Barrel and TAPS detectors were combined to a photon detector system of almost 4π geometrical acceptance. Differential and total cross-sections are reported. At energies close to the threshold, a flat angular distribution has been observed for the reaction γp → K ⁰π⁰Σ⁺ suggesting dominant s -channel production. Σ^*(1385) and higher-lying hyperon states have been observed. An enhancement in the forward direction in the angular distributions of the reaction γp → K ^*0Σ⁺ indicates a t -channel exchange contribution to the reaction mechanism. The experimental data are in reasonable agreement with recent theoretical predictions.     

Measurements of the absolute branching fractions for D→K̄πe+νe, D→K̄*e+νe and determination of Γ(D+→K̄*0e+νe)/Γ(D+→K̄0e+νe)

Using the data of about 33 pb^-1 collected at and around 3.773 GeV with the BES-II detector at the BEPC collider, we have studied the exclusive semileptonic decays D⁺→K^-π⁺e⁺ν_e, D⁰→K̄⁰π^-e⁺ν_e, D⁺→K̄^*0e⁺ν_e and D⁰→K^*-e⁺ν_e. The absolute branching fractions for the decays are measured to be BF(D⁺→K^-π⁺e⁺ν_e)=(3.50±0.75±0.27)%, BF(D⁰→K̄⁰π^-e⁺ν_e)=(2.61±1.04±0.28)%, BF(D⁺→K̄^*0e⁺ν_e)=(5.06±1.21±0.40)% and BF(D⁰→K^*-e⁺ν_e)=(2.87±1.48±0.39)%. The ratio of the vector to pseudoscalar semileptonic decay rates Γ(D⁺→K̄^*0e⁺ν_e)/Γ(D⁺→K̄⁰e⁺ν_e) is determined to be 0.57±0.17±0.02.     

First measurement of the helicity-dependent γ p?pη differential cross-section

The helicity dependence of the γ p↦pη reaction has been measured for the first time at a center-of-mass angle θ^* _η = 70^° in the photon energy range from 780 MeV to 790 MeV. The experiment, performed at the Mainz microtron MAMI, used a 4π-detector system, a circularly polarized, tagged photon beam, and a longitudinally polarized frozen-spin target. The helicity 3/2 cross-section is found to be small and the results for helicity 1/2 agree with predictions from the MAID analysis. Received: 19 December 2002 / Accepted: 10 March 2003 / Published online: 20 May 2003     

DFT calculation of geometrical structure and electronic absorption spectra for neutral,mono-, and diprotonated forms of Risperidone (Risperdal)

Vertical electronic transitions to singlet valence states of an antipsychotic drug, Risperidone (Risperdal), in its neutral, mono-, and diprotonated forms have been calculated within the time-dependent density functional theory using the PBE0 hybrid functional with the 6–31+G^* basis set. The results of the computations show that the lowest-energy allowed π–π^* electronic excitation is affected by protonation effects, the spectral shifts of this transition being potentially useful to individuate the different forms of risperidone