Collision-energy-resolved Penning ionization electron spectroscopy of styrene, 2-vinylpyridine, and 4-vinylpyridine with He*(23S) metastable atoms

Collisional ionization of styrene (phenylethylene), 2-vinylpyridine, and 4-vinylpyridine with metastable He*(2³S) atoms were studied by means of collision-energy/electron-energy resolved two-dimensional Penning ionization electron spectroscopy. Collision energy dependence of partial ionization cross-sections, which reflects the anisotropic interactions between a He*(2³S) atom and the target molecules, indicates that attractive interaction for the out-of-plane access of a He*(2³S) atom to phenyl group is stronger than that for the out-of-plane access to vinyl group. Moreover, it was found for vinylpyridines that the attractive interaction around π electrons became weaker than that for styrene, and that the attractive interaction for the in-plane access to the nitrogen atom is stronger than that for out-of-plane π-directions. However, in 2-vinylpyridine, the hydrogen atom of vinyl group prevents a He*(2³S) atom from approaching to the nitrogen atom along in-plane directions, and thus the attractive interactions around the nitrogen atom were shielded by the vinyl group. The experimentally observed anisotropic interactions were qualitatively supported with ab initio model interaction potential calculations between a Li (He*(2³S)) atom and the target molecule. Concerning with electronic structures of investigated molecules, the assignment of Penning ionization electron spectrum for 4-vinylpyridine was discussed on the basis of different behavior of collision-energy dependence of partial ionization cross-sections, and the satellite ionization band in Penning ionization electron spectra was also reported for styrene.     

Energy dependence of the Penning ionization electron spectrum of Ne* (3P2,0)+Kr

A crossed beam experiment is carried out to measure the energy of electrons emitted in Penning ionization processes by Ne^*(³P_2,0)–Kr collisions. The electron energy spectra have been measured at four different collision energies: 0.050, 0.140, 0.190, 0.460 eV. The analysis of the results allows the separation of spin orbit contributions both in the entrance and in the exit channels providing the related cross-section ratios. Some theoretical considerations have been made to clarify nature and role of interatomic potentials driving the collisions and some general features about the role of atomic fine structure in the Penning ionization processes.     

Two-dimensional Penning ionization electron spectroscopic study on outer characteristics of molecules

Collision-energy/electron-energy-resolved two-dimensional Penning ionization electron spectroscopy (2D-PIES) has been used to study outer characteristics of molecules. Anisotropic potential energy surfaces for collisional ionization of molecules with a metastable helium atom He*(2³S) have been determined starting from ab initio model potentials via optimization based on trajectory calculations. Since ionization widths in the theoretical model of Penning ionization are functionals of target molecular orbitals, outer electron distributions of molecular orbitals can be determined via optimization procedures of calculated ionization cross-sections by trajectory calculations with respect to observed 2D-PIES data.     

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     

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.     

Electron Transitions during the Capture of an Electron by a He<Superscript>2+</Superscript> Ion at the Argon Atom

We have measured the absolute values of the total cross section of the one-electron capture by He²⁺ ions in the kinetic energy range 2–30 keV at the Ar atoms. The absolute values of the differential scattering cross sections of He⁺ ions formed during the one-electron capture and the electron capture with ionization at energies of 2.2, 5.4, and 30 keV have been determined. The electronic states of the formed ions have been determined using collision spectroscopy based on analysis of the change in the kinetic energy of He⁺ after the interaction. We have measured doubly differential (with respect to the kinetic energy and the scattering angle) cross sections of the formation of free electrons. The free electron formation channels (direct ionization and electron capture with ionization) have been analyzed by calculating the electron terms of the (HeAr)²⁺ system. The calculated cross section of capture with ionization is in conformity with the cross section measured using collision spectroscopy.     

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.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

A Clear Atomic Example for the Surface Sensitivity of Penning Ionization: He*(23S) + Yb

Using a crossed-beam apparatus with a double hemispherical electron spectrometer, we have studied the spectrum of electrons released in thermal energy ionizing collisions of metastable He*(2³S) atoms with ground state Yb(4f¹⁴ 6s^{2 1}S₀) atoms, thereby providing the first Penning electron spectrum of an atomic target with 4f-electrons. In contrast to the Hel (58.4 nm) and NeI (73.6/74.4 nm) photoelectron spectra of Yb, which show mainly 4f- and 6s-electron emission in about a 5:1 ratio, the He*(2³S) Penning electron spectrum is dominated by 6s-ionization, accompanied by some correlation-induced 6p-emission (8% Yb⁺(4f¹⁴ 6p ²P) formation) and very little 4f-ionization (?2.5%). This astounding result is attributed to the electron exchange mechanism for He*(2³S) ionization and reflects the poor overlap of the target 4f-electron wavefunction with the 1s-hole of He*(2³S), as discussed on the basis of Dirac-Fock wave functions for the Yb orbitals and through calculations of the partial ionization cross sections involving semiempirical complex potentials. The presented case may be regarded as the clearest atomic example for the surface sensitivity of He*(2³S) Penning ionization observed so far.     

Properties of isolated DNA bases, base pairs and nucleosides examined by laser spectroscopy

The vibronic spectra of laser desorbed and jet cooled guanine (G) adenine (A), and cytosine (C) consist of bands from four, two and two major tautomers respectively, as revealed by UV-UV and IR-UV double resonance spectroscopy. The vibronic spectrum of adenine around 277 nm consists of weak nπ^* and strong ππ^* transitions, based on IR-UV and deuteration experiments. Precise ionization potentials of G and A were determined with 2-color, 2-photon ionization. We also measured vibronic and IR spectra of several base pairs. GC exhibits a HNH ^... OH/NH ^... N/C=O ^... HNH bonding similar to the Watson-Crick GC base pair but with C as enol tautomer. One GG isomer exhibits non-symmetric hydrogen bonding with HNH ^... N/NH ^... N/C=O ^... HNH interactions. A second observed GG isomer has a symmetrical hydrogen bond arrangement with C=O ^... NH/NH ^... O=C bonding. Two CC isomers were observed with symmetrical C=O ^... NH/NH ^... O=C bonding and nonsymmetrical C=O ^... HNH/NH ^... N interaction, respectively. Guanosine (Gs), 2-DeoxyGs und 3-DeoxyGs each exhibit only one isomer in the investigated wavelength range around 290 nm with a strong intramolecular sugar(5-OH) ^... enolguanine(3-N) hydrogen bond. Received 16 June 2002 / Received in final form 15 July 2002 Published online 13 September 2002     

Vibrational inelastic electron-H<Subscript>2</Subscript> scattering revisited: numerically converged coupled channels space frame calculations with model interactions

The collisional excitation of the lower vibrational levels of H₂(¹Σ_g⁺) molecules by low-energy electron impact is computed using an empirical model potential and by solving the coupled-channels scattering equations within a space-fixed (SF) frame of reference formulation. Numerically converged partial, integral inelastic and elastic cross-sections are obtained from what is an essentially exact treatment of the dynamics and the results are compared with measurements and with earlier calculations on the same system. The usefulness of the SF method for handling excitation processes at near-threshold collision energies is discussed and analyzed through the calculations of collisional superelastic partial cross-sections down to 10^-2 meV of collision energy.     

Electron spectroscopy using excited atoms and photons: II. Penning ionization of diatomic molecules

A high resolution electrostatic electron analyser has been used to study Penning ionization electron spectra of H₂, HD, D₂, N₂, CO, NO and O₂ using helium metastable atoms (2¹S, 2³S). Results for H₂, N₂ and CO are in good agreement with other work. New data are presented for HD, D₂, NO and O₂. The Penning electron spectra are also compared to the 584 Å photoelectron spectra obtained in the same apparatus. The relative vibrational intensifies for the given electronic bands indicate that in most cases Franck—Condon factors for Penning ionization and photoionization are very similar. However for the O₂⁺(X²Π_g) band, the (2³S) Penning electron and photoelectron spectra show significant differences in the Franck—Condon envelopes This perturbation of the envelope for the Penning ionization may be explained by a competing autoionization process. The relative electronic transition probabilities are in many cases found to be different for Penning ionization and photoionization.     

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     

Optical and electrochemical properties of cyclometalated Rh(III) complexes based on 4,6-diphenylpyrimidine with ethylenediamine, 2,2′-bipyridyl,and 1,10-phenanthroline

The [Rh(Hdp)₂(N∧N)]ClO₄ complexes (Hdp⁻ is the monodeprotonated form of 4,6-diphenylpyrimidine and (N∧N) is ethylenediamine, 2,2′-bipyridyl, and 1,10-phenanthroline) are synthesized and characterized by ¹H and ¹³C NMR, IR, electronic absorption, and emission spectroscopy, as well as by cyclic voltammetry. The magnetic equivalence of two cyclometalated 4,6-diphenylpyrimidine ligands in the composition of complexes points to the cis position of metalated phenyl rings in the inner sphere. Quasi-reversible one-electron reduction waves are attributed to the ligand-centered electron transfer to the π* antibonding orbital of heterocyclic ligands, while irreversible oxidation waves are associated with electron detachment from the Rh-C σ bonding orbital of the {Rh(Hdp)₂} metal-complex fragment. The characteristic long-wave-length absorption bands and the vibrationally structured phosphorescence bands of complexes are assigned to the spin-allowed and spin-forbidden charge-transfer optical transitions between the σ_Rh-C and π_Hdp* orbitals localized on the {Rh(Hdp)₂} fragment of the complex.     

Study of K<Superscript>*</Superscript><Subscript>0</Subscript>(1430) and a<Subscript>0</Subscript>(980) from B→K<Superscript>*</Superscript><Subscript>0</Subscript>(1430)π and B→a<Subscript>0</Subscript>(980)K decays

We use the decay modes B→K^* ₀(1430)π and B→a₀(980)K to study the scalar mesons K^* ₀(1430) and a₀(980) within the framework of perturbative QCD. For B→K^* ₀(1430)π, we perform our calculation in two scenarios for the scalar meson spectrum. The results indicate that scenario II is more favored by the experimental data than scenario I. The important contribution from annihilation diagrams can enhance the branching ratios by about 50% in scenario I and about 30% in scenario II. The direct CP-asymmetries in B→K^* ₀(1430)π are small, which is consistent with the present experiments. The predicted branching ratio of B→a₀(980)K in scenario I differs from the experiments by a factor of 2, which indicates that a₀(980) cannot be interpreted as q̄q.     

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     

Partial wave analysis of πproduction in two-photon collisions at LEP

The reaction γγ → π⁺π^-π⁰ with quasi-real photons is studied with a total integrated luminosity of 663pb^-1, collected by the L3 detector at LEP at center-of-mass energies from 183 to 209GeV. The results of an energy-dependent partial wave analysis in the mass region 1.1≤M(π⁺π^-π⁰)≤2.2GeV are presented. The reaction is dominated by a₂(1320) formation. A strong signal consistent with the first radial excitation of the isovector tensor state, a₂(1700), is present and confirms the previous L3 observation. Its two-photon partial width is found to be Br(3π) = 0.37^+0.12_-0.08keV, the relative branching ratio of ρ(770)π to f₂(1270)π is 3.4±0.4. For all observed states the product of γγ partial width and 3π branching ratios is measured.     

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     

Determination of electron affinity of electron accepting molecules

The unoccupied π ^* states of the solid film of electron accepting organic molecules, 7,7,8,8-tetracyanoquinodimethane (TCNQ), fluorinated TCNQ derivatives, 11,11,12,12-tetracyanonaphtho-2,6-quinodimethane (TNAP), C₆₀, and 6,6-phenyl-C₆₁-butyric acid methyl ester (PCBM) have been studied by inverse photoemission spectroscopy. The assignment of the π ^* affinity levels of these typical electron accepting molecules provides the basic information for the organic electronics and the new electronic functional molecular design. The comparison with density functional theory calculations enables understanding how the electron affinity evolves in terms of molecular orbitals. The correlation between the film morphology and the irradiation damage on the TCNQ derivative samples by electron impact during the inverse photoemission measurements is also discussed.     

Bottomonium γ(5<Emphasis Type="Italic">S</Emphasis>) decays into <Emphasis Type="Italic">BB</Emphasis> and <Emphasis Type="Italic">BB</Emphasis>π

Two-and three-body decays of γ(5S) into BB, BB*, B*B*, B _s B _s , B _s B _s ^*, and BB*π, B*B*π are evaluated using the theory developed earlier for dipion-bottomonium transitions. The theory contains only two parameters—vertex masses M _br and M _ω—known from the dipion spectra and width. Predicted values of Γ_tot(5S) and six partial widths Γ _k (5S), k = BB, BB*, ... are in agreement with the experiment. The decay widths Γ_5S (πBB*) and Γ_5S (πB*B*) are also calculated and found to be on the order of 10 keV. The text was submitted by the authors in English.