Excimer emission spectrum in noble gas systems

A simple expression for the time shape of excimer emission as a function of temperature is obtained for the case of a realistic (exponential) ground state potential. The excimer binding energy and its equilibrium geometry are obtained for the lowest ¹Σ_u states of Ar*₂, Kr*₂, Xe*₂ and for the A¹Σ_u and D¹Σ_u states of Hc*₂, by comparing the theoretical formula with the corresponding experamental results. Agreement with electronic calculations when available of these parameter is very good. The relation between our line-shape expression and those given by other authors is discussed.     

Time-resolved excitation spectra of xenon vapor in the 1500 Å region

Time-integrated and time-resolved excitation spectra, as well as fluorescence lifetimes, have been measured for xenon vapor as a funtion of pressure (for pure xenon as well as with different collision partners: krypton and helium), monitoring the 1700 Å second continuum afterglow. Three very different decay components have been observed: (a) A short component with lifetimes of the order of 2 ns, which is attributed to emission from the upper vibrational levels of the O⁺_u(¹Σ⁺_u) state of Xe*₂. (b) A long component with τ ≈ 60 ns, corresponding to emission from thermally relaxed vibrational levels of the 1_u,O^?_u(³Σ⁺_u) states of Xe*₂. No intervention of any Xe atomic excited species is invoked to explain the excitation and deactivation processes of Xe₂ molecules for these two components of the fluorescence. (c) A very long component with lifetimes in the 150–500 ns range, having a broad ? 1000 cm^?1 - excitation band, centered at ≈ 1470 Å and showing a striking screening and self-absorption effect as well as a strong effect when the partial pressure of a collision partner (Kr, He) is increased. The mechanism of this last excitation is not yet very well understood.     

The Role of the nπ* 1Au State in the Photoabsorption and Relaxation of Pyrazine

The geometric, energetic, and spectroscopic properties of the ground state and the lowest four singlet excited states of pyrazine have been studied by using DFT/TD‐DFT, CASSCF, CASPT2, and related quantum chemical calculations. The second singlet nπ* state, ¹A_u, which is conventionally regarded dark due to the dipole‐forbidden ¹A_u←¹A_g transition, has been investigated in detail. Our new simulation has shown that the state could be visible in the absorption spectrum by intensity borrowing from neighboring nπ* ¹B_3u and ππ* ¹B_2u states through vibronic coupling. The scans on potential‐energy surfaces further indicated that the ¹A_u state intersects with the ¹B_2u states near the equilibrium of the latter, thus implying its participation in the ultrafast relaxation process.     

Fluorescence of Xe2 molecules in the vacuum-ultraviolet

Fluorescence of the Xe₂ continuum between 1460 and 1800 Å has been observed during excitation of Xe₂ molecules with CO fourth positive bands from a microwave discharge lamp. Fluorescence spectra at different Xe and added gas pressures show that in collisions with Xe or Kr atoms, the excited Xe₂ diatoms are efficiently relaxed to low vibrational levels of the ¹Σ_u⁺ and ³Σ_u⁺ potentials without being quenched noticeably. With Kr the rate constant for relaxation out of the primarily excited high vibrational levels is found to be about 3×10^?11 cm³ molecule^?1 s^?1.     

Electron energy-loss vibronic spectroscopy of matrix-isolated benzene and multilayer benzene films

Electronic transitions near the surface of benzene multilayer films (50–100 A) and in Xe matrices containing 2% benzene have been studied by high-resolution electron energy-loss spectroscopy at primary energies between 5 and 14 eV. The lowest three transitions exhibit vibrational structure that can be ascribed to the ³E_1u³B_1u³B_2u free-molecule configurations of C₆H₆.     

Photoionization of Xe2, Xe3 and Xe4 in the 1024–1113 Å region

The mass spectra of Xe _n ⁺ clusters (n=2–13) were recorded using a supersonic beam and an ion time-of-flight mass analyser. The yield of Xe ₂ ⁺ , Xe ₃ ⁺ and Xe ₄ ⁺ cluster ions was measured with a resolution of 0.1 Å (1 meV) in the 1024–1113 Å (11.1–12.1 eV) region. Autoionizing Rydberg series of Xe₂ converging to theC ²_3/2u state of Xe ₂ ⁺ were observed in the spectrum of Xe ₂ ⁺ . The photoionization yield of Xe ₃ ⁺ and Xe ₄ ⁺ ions each displayed similar broad features that contained no fine structure corresponding to vibrational states. The broad features were assigned to autoionizing Rydberg series by analogy with the dimer ion spectrum.     

Multi-reference configuration interaction calculations on the systems Xe 2 + and Xe 3 +

Potential curves for the ground (²Σ _u ⁺ ) and the three lowest excited states of the Xe ₂ ⁺ dimer ion (²Π _g ,²Π _u ,²Σ _g ⁺ ) have been calculated using pseudopotentials in MRD-CI (multi-reference single anddouble excitationconfigurationinteraction) calculations. Spin-orbit interaction — leading to the six states 1.(1/2) _u , 1.(3/2) _g , 1.(3/2) _u , 1.(1/2) _g , 2.(1/2) _u , 2.(1/2) _g — has been taken into account using a semiempirical technique [1]. Subsequently, starting with a relaxed Xe ₂ ⁺ ion in its ground state, the potential energy surface for the system Xe-Xe ₂ ⁺ was studied. We found that the collinear approach of the Xe atom leads to the most stable geometry. This is a linear symmetric molecule with bond lengths of 6.38 bohr. In the bestT-shaped structure, the Xe atom is 7.83 bohr away from the midpoint of the Xe ₂ ⁺ (r=6.1 bohr) dimer. The calculated binding energy of 0.25 eV for the equilibrium structure of the Xe ₃ ⁺ molecule (i.e. the linear symmetric geometry), is in very good agreement with experimental results of 0.27 ± 0.02 eV [2].     

On xenon molecule excited state lifetimes

Time-resolved excitation spectra of xenon vapor in the 150 nm region are analysed in terms of four main fluorescence lifetimes corresponding to decays of four stable excited electronic states of the Xe dimer. The two shortest decay times, ≈ 2 ns and ≈ 60 ns, are assigned to the direct radiative relaxation of the two lowest excited ungerade states, (¹Σ⁺_u)0⁺_u and (³Σ⁺_u))1 u respectively. The two longest decay times, ≈ 150 ns and ≈ 500 ns, must correspond to the overall depopulation rates of the two lowest excited gerade states, (³Σ⁺_g)1g and (¹Σ⁺_g)0⁺_g, decaying into the gerade ground state by cascading down through the intermediate ungerade states.     

A photoionization study of the charge transfer reactions: Xe+ + O2 → O+2 + Xe and O+2 + Xe → Xe+ + O2

Photoionization mass spectrometer techniques have been employed to study the charge transfer reactions: Xe⁺ + O₂ → O⁺₂ + Xe and O⁺₂ + Xe → Xe⁺ + O₂. The results show the reaction of Xe⁺(²P_{$\text{3}\text{2}$}) ions with O₂ molecules is much more efficient than the reaction of Xe⁺(²P_{$\text{1}\text{2}$}) ions with O₂ molecules. The charge transfer reaction of O⁺₂ ions with Xe atoms was detected for O⁺₂ ions in the a ⁴Π_u state.     

Molecular beam kinetics: The excitation function of the reaction Xe(3P0,2) + Br2 → XeBr* + Br

Fast beams of metastable xenon atoms, Xe(³P_0,2), have been generated by combining the high speed rotor technique with electron bombardment excitation. In a crossed-beam apparatus, the excitation function σ(E_t) of the reaction Xe(³P_0,2) + Br₂ → XeBr* + Br has been measured. The results show a close similarity to the behaviour of the alkali metal atoms, with which the metastable rate gas atoms have been previously compared.     

Experimental and theoretical studies of the valence-shell dipole excitation spectrum of molecular fluorine

Electron energy loss measurements and concommitant RPAE calculations are reported of the valence-shell dipole excitation spectrum of molecular fluorine. The measured spectrum is dominated by a series of strong features in the 12–16 eV interval which are in accord with X¹Σ_g⁺→¹Σ_u⁺ bands assigned in a previously reported high-resolution optical study. These features are attributed on basis of the present RPAE calculations to configuration mixing between 1π_g→npπ_u Rydberg and 3σ_g→3σ_u intravalence excitations. A depleted X→V_σ charge-transfer excitation is correspondingly observed at ≈17 eV, in good accord with the calculated values. The appearance of the σ→σ* transition in F₂ below the 3σ_g^?1 threshold is in marked contrast to the situation in other light diatomic molecules, in which cases σ→σ* transitions appear as intravalence shape resonances in photoionization continua. Assignments are also provided of weak, irregularly spaced X¹Σ_g⁺→¹Π_u excitations the origins of which are attributed to configuration mixing between 1π_g→npσ_u and 1π_u→nsσ_g Rydberg series.     

Electronic structure of the azide ion using the SCF Xα SW method

The electronic structure of the azide ion is investigated using the SCF Xα scattered wave method. Calculated ionization energies are compared with values determined by electron spectroscopy. Transition state calculations for π_g → π*_u, σ_u → π*_u and σ_g → π*_u single electron transitions yield excitation energies near 5.7, 11.0, and 12.0 eV respectively.     

Spectroscopy and kinetics of the 1P1 and 3P2 states of Hg 6s6p in xenon

The spectra and kinetics observed following excitation of Hg 6s6p(¹P₁) in xenon show the occurence of complex attachment and relaxation processes. The ¹P₁ attaches to Xe in termolecular collisions to produce HgXe E¹1, which emits a broad band with λ_max ≈ 2150 Å. Addition of krypton to Hg, Xe mixtures enhances the E-state emission by atom exchange with an HgKr^* complex. The E state also undergoes collisional deactivation by Xe, rate coefficient (1.75 ± 0.25) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, to generate ³P₂. However, the predominant route for ³P₂ formation is via collision of ¹P₁ with Xe, rate coefficient ≈ 4 × 10⁻¹² cm³ molecule⁻¹ s⁻¹. With [Xe] at 760 Torr, about 75% of the generated ³P₂ is attached in the form of the HgXe(C ³2) complex; lifetimes up to 600 μs have been observed. Two new emission bands occur when ³P₂ is prepared in xenon. A sharp feature, slightly blue-shifted from the forbidden ³P₂:¹S₀ line, results when ³P₂ and Xe approach on the D ³1 surface. The other band is broad with λ_max ≈ 2520 Å; the carrier is assigned to an HgXe₂(³2_u) complex. Rate coefficients for deactivation of ³P₂ to lower ³P_J states have been measured.     

Time and spectrally resolved fluorescence of Cl*2 and ArCl* in Cl2 doped Ar Under state selective pulsed photoexcitation with synchrotron radiation

Synchrotron Radiation is used to selectively excite chlorine and Cl₂ doped argon in the VUV region. Stationary fluorescence and excitation spectra of the 1¹Σ _u ⁺ , 2¹Σ _u ⁺ and 2³Πg Cl ₂ ^* states and of the ArCl*(B?X) transition are obtained. The excitation threshold of ArCl*(B) in Ar/Cl₂ system is found to be 1,285±5 Å and that of ArCl(C) at ～1,260 Å. The formation of ArCl* and Cl*₂(2³Πg) is discussed in terms of recent potential curves data. A detailed time resolved study is reported which allows us to determine precisely the radiative lifetime of ArCl*(B) state (5.2 ns) and numerous kinetic parameters of this system, to estimate theC state energy and to discuss the relaxation and mixing process of the ArCl*(B) and (C) states. A two ladder multilevel kinetic model is described which accounts for the experimental results and shows the difficulty of studying this particular ArCl* system as compared to the closely related XeCl* and KrCl* ones.     

Determination of 131mXe and 133mXe in the presence of 133gXe via combined beta-spectroscopy and delayed coincidence

The International Monitoring System for the Comprehensive Nuclear-Test-Ban Treaty will include measurements of Xe fission products. Pacific Northwest National Laboratory has developed an automated system for separating Xe from air which detects Xe fission products using a beta-gamma counting system for ^131mXe, ^133mXe, ^133gXe, and ^135gXe. Betas and conversion electrons are detected in a plastic scintillation cell containing the Xe sample. Gamma and X-rays are detected in a NaI(Tl) scintillation detector which surrounds the plastic scintillator sample cell. Two-dimensional pulse-height spectra of gamma-energy versus beta-energy are obtained. The plastic scintillator spectrum in coincidence with the 31-keV X-rays from ^131mXe. ^133mXe, and ^133gXe is a complex mixture of conversion electrons and betas. A new technique to simultaneously measure the delayed coincidence (T _1/2 = 6.27 ns) between beta-particles from ^133gXe and conversion electrons depopulating the 81-keV state in 133 Cs is being developed. This technique allows separation of the ^133gXe beta spectrum from the conversion electrons due to ^131mXe and ^133mXe and uniquely quantifies all three nuclides.     

Frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group

The frontier orbital interactions of electron pushing and drawing substituents with ferrocenyl group were analyzed based on the electrochemical,UV visible spectral and spectroelectrochemical results of five ferrocene derivatives,R-Fc-A1(PⅠ),A1-Fc-A1(PⅡ),D-Fc-R (PⅢ),D-Kc-A1(PIV) and D-Fc-A2(PV)(R,CH2OH;A1 CHO;A2,CH=C(CN)2 and D,(C18H37)2N-C6H4-CH=CH) It was found that there are strong interactions of the LUMO (πA) of electron drawing substituents with le2g(dxy,dx2 y2)and e2u of the ferroeenyl group because the energy levels of πA and e2g,C2U of (Cp )2 are close,which lower not only the energy levels of bonded orbits,πA+ and dx2-y2+[πA] of PⅠ,PⅡ,PⅣ and PⅤobviously,but also those of their non-bonded orbu dxy For PⅢ,PⅣ and PⅤ,there are strong interactions of HOMO(πD) of the electron pushing substituent with le of the ferrocenyl group because the levels of πD and e of (Cp)2 are close,which result in the formation of anti-bonded orbit,πD- and bonded orbit     

Collisional quenching of resonance states of rare gases

We report an experimental study of Xe(³P₁) → Xe(³P₂) electronic quenching by Ar in Xe/Ar mixtures optically excited by the 1470 Å line of Xe. The quenching process was monitored by the observation of the Xe^*₂ second emission continuum at low Xe pressures.     

129Xe-Kernresonanzuntersuchungen von Xenonverbindungen. II. Xenon(II)-Derivate

¹²⁹-Xe-NMR Spectra of Xenon Compounds. II Xenon (II) Compounds The ¹²⁹Xe NMR Spectra of Xe(OSeF₅)₂, Xe(OTeF₅)₂, FXe–OSeF₅, FXe–OTeF₅, and F₅SeO–Xe–OTeF₅ have been measured and discussed. The mixed compounds FXe–OSeF₅, FXe–OSeF₅, FXe–OTeF₅, and F₅SeO–Xe–OTeF₅ exist only in equilibrium with the derivatives Xe(OSeF₅)₂, Xe(OTeF₅)₂ and XeF₂. Coupling of ¹²⁹Xe is observed with the fluorine directly bonded at the Xenon atom, with the equatorial fluorine atoms on selenium and tellurium. and with the tellurium isotop ¹²⁵Te.     

129Xe and 131Xe nuclear magnetic dipole moments from gas phase NMR spectra

³He, ¹²⁹Xe and ¹³¹Xe NMR measurements of resonance frequencies in the magnetic field B₀ = 11.7586 T in different gas phase mixtures have been reported. Precise radiofrequency values were extrapolated to the zero gas pressure limit. These results combined with new quantum chemical values of helium and xenon nuclear magnetic shielding constants were used to determine new accurate nuclear magnetic moments of ¹²⁹Xe and ¹³¹Xe in terms of that of the ³He nucleus. They are as follows: μ(¹²⁹Xe) = ?0.7779607(158)μ_N and μ(¹³¹Xe) = +0.6918451(70)μ_N. By this means, the new ‘helium method’ for estimations of nuclear dipole moments was successfully tested. Gas phase NMR spectra demonstrate the weak intermolecular interactions observed on the ³He and ¹²⁹Xe and ¹³¹Xe shielding in the gaseous mixtures with Xe, CO₂ and SF₆. Copyright © 2015 John Wiley & Sons, Ltd.     

Laser photoionization of metastable Xe* (J=0) atoms in the range 462–430 nm

Absolute cross sections for photoionization of metastable Xe* (5p ⁵ 6s′³ P ₀) atoms are presented over the wavelength range 462–430 nm (photoelectron energy ε=0–200 meV), including the 7p′[3/2]₁ and 7p′[1/2]₁ autoionization resonances. In addition the angular distribution of the photoelectrons is reported across the 7p′ resonances (ε=90–180 meV). The experimental data are compared with Hartree-Fock calculations of the photoionization process.