Spectroscopy of alkali atoms (Li,Na, K) attached to large helium clusters

Large liquid helium clusters (He_n, n ≈ 10⁴) produced in a supersonic jet are doped with alkali atoms (Li, Na, K) and characterized by means of laser induced fluorescence. Each cluster contains, on average, less than one dopant atom. Both excitation and emission spectra have been recorded. The observed excitation spectra are analyzed, calculating the transitions within an approach based on the hypothesis that the chromophores are trapped in a dimple on the cluster’s surface as predicted by the theoretical calculations of Ancilotto et al. [9]. The results of the model calculations are in good qualitative agreement with the experimental findings. In spite of the very weak binding energy (a few cm^?1), some of the excited atoms remain bound to the surface, provided the excitation occurs at frequencies not too far from the alkali’s gas phase absorptions. These bound-bound excitations produce very broad, red shifted emission spectra. At other, blue shifted frequencies, the excited atoms desorb from the cluster’s surface, giving rise to unshifted, free atom, emission spectra. The heavier alkali metals (Na, K) show, compared to the calculations, an additional broadening which is attributed to surface excitations on the helium droplet.     

Energy transfer in collisions of excited Ar(3P0.2) metastable atoms with H(2S) atoms. II. Lyman-α emission profile

Spectra of the Lyman-α emission resulting from the Ar(4s, ³P_2.0) + H(Is, ²S) interaction have been recorded. The emission line profile is essentially rectangular with a full width of 13 pm. These results show that excited H(n = 2) atoms are formed in the reaction, with nearly all the excess energy (1.34 eV) appearing as kinetic energy of the hydrogen atom. Lyman-α emission profiles also have been obtained from microwave discharge plasmas in argon and helium, containing traces of hydrogen; these profiles are compared with those from the Ar(³P_2.0) + H(²S) system.     

The selective determination of halogens and sulphur in solution by atmospheric-pressure helium microwave-induced plasma emission spectrometry coupled to an electrothermal introduction system

Instrumentation is described for the direct determination of Cl, Br, I and S in dissolved samples. A tantalum furnace is coupled directly to a TM₀₁₀ cavity, in which a helium microwave plasma is generated at atmospheric pressure. Samples (20 μl) are dried, ashed and atomized; the free atoms are transported by helium to the cavity, where they are excited. Detection limits are in the sub-mg l^-1 region. The effect of counter cations is removed by the addition of 50 mg l^-1 potassium hydroxide, which also helps to suppress interferences by large amounts of matrix constituents, but the standard addition technique remains necessary to permit determinations that are reliable to within 5%.     

Spatially Dependent Kinetics of Electrons and Excited Atoms in the Column Plasma of a He–Xe dc Discharge

The radially varying kinetics of electrons and excited atoms in the cylindrical axially homogeneous positive column of a dc glow discharge in a gas mixture of helium and 2% xenon was studied. The experimental investigations comprise the radially resolved measurements of the isotropic part of the electron velocity distribution function (EVDF) using a single-probe technique and of the densities of atoms in the lower excited states by using a laser diode absorption method. The theoretical investigations are based on the solution of the space-dependent kinetic equation for the EVDF and the balance equations of excited gas atoms. Besides a strict solution, various simplified treatments of the electron kinetics as the conventional homogeneous approach and the nonlocal approach have been applied. The electron kinetic behavior in the helium–xenon column plasma changes remarkably with increasing helium gas pressure from a distinctly nonlocal behavior at a low pressure of 100 Pa to a nearly local behavior at a medium pressure of 600 Pa.     

Hydrogen analysis in solid samples by utilizing He metastable atoms induced by TEA CO2 laser plasma in He gas at 1 atm

A TEA CO₂ laser (350 mJ–1.5 J, 10.6 μm, 200 ns, 10 Hz) was focused onto a metal sub-target under He as host gas at 1 atmospheric pressure with a small amount of impurity gas, such as water and ethanol vapors. It was found that the TEA CO₂ laser with the help of the metal sub-target is favorable for generating a strong, large volume helium gas breakdown plasma at 1 atmospheric pressure, in which the helium metastable-excited state was then produced overwhelmingly. While the metal sub-target itself was never ablated. The helium metastable-excited state produced after the strong helium gas breakdown plasma was considered to play an important role in exciting the atoms. This was confirmed by the specific characteristics of the detected H emission, namely the strong intensity with low background, narrow spectral width, and the long lifetime. This technique can be used for gas and solid samples analysis. For nonmetal solid analysis, a metal mesh was introduced in front of the nonmetal sample surface to help initiation of the helium gas breakdown plasma. For metal sample, analysis can be carried out by combining the TEA CO₂ laser and an Nd–YAG laser where the Nd–YAG laser is used to ablate the metal sample. The ablated atoms from the metal sample are then sent into the region of helium gas breakdown plasma induced by the TEA CO₂ laser to be excited through the helium metastable-excited state. This technique can be extended to the analysis of other elements, not limited only to hydrogen, such as halogens.     

Emission spectroscopic studies of Grimm-type glow discharge plasma with argon-helium gas mixtures

The effect of argon/helium pressure ratios on the emission intensity of various Ar II lines is investigated for a Grimm-type glow discharge radiation source, operated with Ar-He mixtures. The relative intensities of the Ar II lines are altered significantly by mixing helium with argon. It is found that the population of the Ar⁺ excited states can be redistributed through He-Ar collisional energy transfer. The energy level of the He singlet metastable state (¹S₀,20.62 eV) is very important for these processes. If the excitation energy of Ar II lines is higher than that of the He singlet metastable, strong quenching of the Ar II line intensity is observed. However, when the excitation energy is slightly lower, some of the Ar II lines are enhanced by adding helium to the argon plasma. Energy exchanges between the Ar⁺ doublet term states and the He singlet metastable are favoured because the total spin remains unchanged before and after the He-Ar collisions. Furthermore, the helium mixing also exerts a great influence on the emission intensities of the elements sputtered from the cathode of the discharge lamp. The enhancement of Al I and Al II emission intensities at suitable Ar-He mixture ratios is discussed for when aluminum is employed as a cathode material.     

Synthesis,Structural Characterization,Photophysics, and Broadband Nonlinear Absorption of a Platinum(II) Complex with the 6‐(7‐Benzothiazol‐2′‐yl‐9,9‐diethyl‐9 H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl Ligand

A platinum complex with the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl ligand ( 1 ) was synthesized and the crystal structure was determined. UV/Vis absorption, emission, and transient difference absorption of 1 were systematically investigated. DFT calculations were carried out on 1 to characterize the electronic ground state and aid in the understanding of the nature of low‐lying excited electronic states. Complex 1 exhibits intense structured ¹π–π* absorption at λ_abs<440 nm, and a broad, moderate ¹M LCT/¹LLCT transition at 440–520 nm in CH₂Cl₂ solution. A structured ³π–π*/³M LCT emission at about 590 nm was observed at room temperature and at 77 K. Complex 1 exhibits both singlet and triplet excited‐state absorption from 450 nm to 750 nm, which are tentatively attributed to the ¹π–π* and ³π–π* excited states of the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridine ligand, respectively. Z‐scan experiments were conducted by using ns and ps pulses at 532 nm, and ps pulses at a variety of visible and near‐IR wavelengths. The experimental data were fitted by a five‐level model by using the excited‐state parameters obtained from the photophysical study to deduce the effective singlet and triplet excited‐state absorption cross sections in the visible spectral region and the effective two‐photon absorption cross sections in the near‐IR region. Our results demonstrate that 1 possesses large ratios of excited‐state absorption cross sections relative to that of the ground‐state in the visible spectral region; this results in a remarkable degree of reverse saturable absorption from 1 in CH₂Cl₂ solution illuminated by ns laser pulses at 532 nm. The two‐photon absorption cross sections in the near‐IR region for 1 are among the largest values reported for platinum complexes. Therefore, 1 is an excellent, broadband, nonlinear absorbing material that exhibits strong reverse saturable absorption in the visible spectral region and large two‐photon‐assisted excited‐state absorption in the near‐IR region.     

Beryllium Atom Mediated Dinitrogen Activation via Coupling with Carbon Monoxide

The reactions of laser‐ablated beryllium atoms with dinitrogen and carbon monoxide mixtures form the end‐on bonded NNBeCO and side‐on bonded (η²‐N₂)BeCO isomers in solid argon, which are predicted by quantum chemical calculations to be almost isoenergetic. The end‐on bonded complex has a triplet ground state while the side‐on bonded isomer has a singlet electronic ground state. The complexes rearrange to the energetically lowest lying NBeNCO isomer upon visible light excitation, which is characterized to be an isocyanate complex of a nitrene derivative with a triplet electronic ground state. A bonding analysis using a charge‐ and energy decomposition procedure reveals that the electronic reference state of Be in the NNBeCO isomers has an 2s⁰2p² excited configuration and that the metal‐ligand bonds can be described in terms of N₂→Be←CO σ donation and concomitant N₂←Be→CO π backdonation. The results demonstrate that the activation of N₂ with the N?N bond being completely cleaved can be achieved via coupling with carbon monoxide mediated by a main group atom.     

Highly Efficient Triplet Photosensitizers: A Systematic Approach to the Application of IrIII Complexes containing Extended Phenanthrolines

A series of Ir^III complexes, based on 1,10‐phenanthroline featuring aryl acetylene chromophores, were prepared and investigated as triplet photosensitizers. The complexes were synthesized by Sonogashira cross‐coupling reactions using a “chemistry‐on‐the‐complex” method. The absorption properties and luminescence lifetimes were successfully tuned by controlling the number and type of light‐harvesting group. Intense UV/Vis absorption was observed for the Ir^III complexes with two light‐harvesting groups at the 3‐ and 8‐positions of the phenanthroline. The asymmetric Ir^III complex (with a triphenylamine (TPA) and a pyrene moiety attached) exhibited the longest lifetime. Red emission was observed for all the complexes in deaerated solutions at room temperature. Their emission at low temperature (77 K) and nanosecond time‐resolved transient difference absorption spectra revealed the origin of their triplet excited states. The singlet‐oxygen (¹O₂) sensitization and triplet‐triplet annihilation (TTA)‐based upconversion were explored. Highly efficient TTA upconversion (Φ_UC=28.1 %) and ¹O₂ sensitization (Φ_Δ=97.0 %) were achieved for the asymmetric Ir^III complex, which showed intense absorption in the visible region (λ_abs=482 nm, ?=50900 m ^?1 cm^?1) and had a long‐lived triplet excited state (53.3 μs at RT).     

Spatially resolved spectroscopic measurements of a dielectric barrier discharge plasma jet applicable for soft ionization

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry and as ionization source for ion mobility spectrometry. It turned out that dielectric barrier discharge ionization could be regarded as a soft ionization technique characterized by only minor fragmentation similar to atmospheric pressure chemical ionization (APCI). Mainly protonated molecules were detected. In order to characterize the soft ionization mechanism spatially resolved optical emission spectrometry (OES) measurements were performed on plasma jets burning either in He or in Ar. Besides to spatial intensity distributions of noble gas spectral lines, in both cases a special attention was paid to lines of N₂⁺ and N₂. The obtained mapping of the plasma jet shows very different number density distributions of relevant excited species. In the case of helium plasma jet, strong N₂⁺ lines were observed. In contrast to that, the intensities of N₂ lines in Ar were below the present detection limit. The positions of N₂⁺ and N₂ distribution maxima in helium indicate the regions where the highest efficiency of the water ionization and the protonation process is expected.     

Spectroscopic characterization of organic cations: emission and laser-excitation spectra of rotationally cooled CH3CCX+, X  Cl,Br

The gas phase emission and laser-excitation spectra of the òE ↔ X̃²E transition of rotationally and vibrationally cooled 1-chloro- and 1-bromopropyne cations, and their fully deuterated analogues, have been obtained. The emission was excited by electron impact on a seeded helium supersonic free jet and the fluorescence by laser-excitation of cations formed by Penning ionization and collisional relaxation of liquid-nitrogen temperature. Comparison of the two sets of data locates the band origins and enables the prominent spectral features to be vibrationally assigned. The vibrational frequencies of many of the fundamentals could be inferred for these cations in their X̃²E and òE states.     

Sampling modulation technique in radio-frequency helium glow discharge emission source by use of pulsed laser ablation

An emission excitation source comprising a high-frequency diode-pumped Q-switched Nd:YAG laser and a radio-frequency powered glow discharge lamp is proposed. In this system sample atoms ablated by the laser irradiation are introduced into the lamp chamber and subsequently excited by the helium glow discharge plasma. The pulsed operation of the laser can produce a cyclic variation in the emission intensities of the sample atoms whereas the plasma gas species emit the radiation continuously. The salient feature of the proposed technique is the selective detection of the laser modulation signal from the rest of the continuous background emissions, which can be achieved with the phase sensitive detection of the lock-in amplifier. The arrangement may be used to estimate the emission intensity of the laser ablated atom, free from the interference of other species present in the plasma. The experiments were conducted with a 13.56 MHz radio-frequency (rf) generator operated at 80 W power to produce plasma and the laser at a wavelength of 1064 nm (pulse duration:34 ns, repetition rate:7 kHz and average pulse energy of about 0.36 mJ) was employed for sample ablation. The measurements resulted in almost complete removal of nitrogen molecular bands (N₂⁺ 391.44 nm). Considerable reduction (about 75%) in the emission intensity of a carbon atomic line (C I 193.03 nm) was also observed.     

The spectral detectability of fluorine in a helium glow discharge

The theoretical basis of the excitation of the fluorine emission spectrum is discussed, and the negative effects of easily excited impurities are demonstrated. Fluorine can be detected by means of its emission spectrum if it is present as a minor impurity in helium. The amount of water vapor and/or organic compounds in the helium must be minimized because these substances produce easily excited fragments in the glow discharge which dissipate the energy needed to excite fluorine atoms. Direct excitation of a diphenyldifluorosilane residue permits detection of about 70 pg of fluorine; if fluorine is volatilized as hydrofluoric acid and injected directly into the glow discharge, a photocurrent peak of 1.8 Ag^-1 of fluorine is obtained.     

Long‐Lived Room‐Temperature Deep‐Red‐Emissive Intraligand Triplet Excited State of Naphthalimide in Cyclometalated IrIII Complexes and its Application in Triplet‐Triplet Annihilation‐Based Upconversion

Cyclometalated Ir^III complexes with acetylide ppy and bpy ligands were prepared (ppy=2‐phenylpyridine, bpy=2,2′‐bipyridine) in which naphthal ( Ir‐2 ) and naphthalimide (NI) were attached onto the ppy ( Ir‐3 ) and bpy ligands ( Ir‐4 ) through acetylide bonds. [Ir(ppy)₃] ( Ir‐1 ) was also prepared as a model complex. Room‐temperature phosphorescence was observed for the complexes; both neutral and cationic complexes Ir‐3 and Ir‐4 showed strong absorption in the visible range (ε=39600 M ^?1 cm^?1 at 402 nm and ε=25100 M ^?1 cm^?1 at 404 nm, respectively), long‐lived triplet excited states (τ_T=9.30 μs and 16.45 μs) and room‐temperature red emission (λ_em=640 nm, Φ_p=1.4 % and λ_em=627 nm, Φ_p=0.3 %; cf. Ir‐1 : ε=16600 M ^?1 cm^?1 at 382 nm, τ_em=1.16 μs, Φ_p=72.6 %). Ir‐3 was strongly phosphorescent in non‐polar solvent (i.e., toluene), but the emission was completely quenched in polar solvents (MeCN). Ir‐4 gave an opposite response to the solvent polarity, that is, stronger phosphorescence in polar solvents than in non‐polar solvents. Emission of Ir‐1 and Ir‐2 was not solvent‐polarity‐dependent. The T₁ excited states of Ir‐2 , Ir‐3 , and Ir‐4 were identified as mainly intraligand triplet excited states (³IL) by their small thermally induced Stokes shifts (ΔE_s), nanosecond time‐resolved transient difference absorption spectroscopy, and spin‐density analysis. The complexes were used as triplet photosensitizers for triplet‐triplet annihilation (TTA) upconversion and quantum yields of 7.1 % and 14.4 % were observed for Ir‐2 and Ir‐3 , respectively, whereas the upconversion was negligible for Ir‐1 and Ir‐4 . These results will be useful for designing visible‐light‐harvesting transition‐metal complexes and for their applications as triplet photosensitizers for photocatalysis, photovoltaics, TTA upconversion, etc.     

Long‐Lived Room‐Temperature Near‐IR Phosphorescence of BODIPY in a Visible‐Light‐Harvesting N^C^N PtII–Acetylide Complex with a Directly Metalated BODIPY Chromophore

Room‐temperature long‐lived near‐IR phosphorescence of boron‐dipyrromethene (BODIPY) was observed (λ_em=770 nm, Φ_P=3.5 %, τ_P=128.4 μs). Our molecular‐design strategy is to attach Pt^II coordination centers directly onto the BODIPY π‐core using acetylide bonds, rather than on the periphery of the BODIPY core, thus maximizing the heavy‐atom effect of Pt^II. In this case, the intersystem crossing (ISC) is facilitated and the radiative decay of the T₁ excited state of BODIPY is observed, that is, the phosphorescence of BODIPY. The complex shows strong absorption in the visible range (ε=53800 M ^?1 cm^?1 at 574 nm), which is rare for Pt^II–acetylide complexes. The complex is dual emissive with ³M LCT emission at 660 nm and the ³IL emission at 770 nm. The T₁ excited state of the complex is mainly localized on the BODIPY moiety (i.e. ³IL state, as determined by steady‐state and time‐resolved spectroscopy, 77 K emission spectra, and spin‐density analysis). The strong visible‐light‐harvesting ability and long‐lived T₁ excite state of the complex were used for triplet‐triplet annihilation based upconversion and an upconversion quantum yield of 5.2 % was observed. The overall upconversion capability (η=ε×Φ_UC) of this complex is remarkable considering its strong absorption. The model complex, without the BODIPY moiety, gives no upconversion under the same experimental conditions. Our work paves the way for access to transition‐metal complexes that show strong absorption of visible light and long‐lived ³IL excited states, which are important for applications in photovoltaics, photocatalysis, and upconversions, etc.     

Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin–orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the 2|H_so|S₁>, 1|H_so|S₁>, and 1|H_so|S₀> spin–orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S₁→T₁ population transfer is found to proceed at a rate of ≈10⁷ s⁻¹ in the isolated molecule.     

Excitation of singly ionized argon species in helium-matrix glow discharge plasma—role of the energy transfer from helium metastables

When a small amount of argon is added to the helium plasma in a Grimm-type glow discharge radiation source, the interaction between helium and argon species is investigated from analyzing the intensities of emission lines of of argon ion (ArII). The excitation energy as well as the term multiplicity concerning the optical transitions to which the ArII emission lines are identified are significant factors for determining their emission intensities in the helium-matrix plasma. In the case where the excitation energy of ArII lines is higher than the internal energy of the helium metastable states, the emission intensity in the helium-matrix plasma is observed to be much weaker than that obtained only with argon gas. On the other hand, the intensity is enhanced when the excitation energy is slightly lower. In the excited levels of argon ion having quartet multiplicity, closer interactions with the triplet rather than the singlet metastable level of helium atom are recognized, with the singlet helium metastable in the argon excited levels having doublet multiplicity.     

Iridium(III) Complexes Bearing Pyrene‐Functionalized 1,10‐Phenanthroline Ligands as Highly Efficient Sensitizers for Triplet–Triplet Annihilation Upconversion

“Chemistry‐on‐the‐complex” synthetic methods have allowed the selective addition of 1‐ethynylpyrene appendages to the 3‐, 5‐, 3,8‐ and 5,6‐positions of Ir^III‐coordinated 1,10‐phenanthroline via Sonogashira cross‐coupling. The resulting suite of complexes has given rise to the first rationalization of their absorption and emission properties as a function of the number and position of the pyrene moieties. Strong absorption in the visible region (e.g. 3,8‐substituted Ir‐3 : λ_abs=481 nm, ?=52 400 m ^?1 cm^?1) and long‐lived triplet excited states (e.g. 5‐substituted Ir‐2 : τ_T=367.7 μs) were observed for the complexes in deaerated CH₂Cl₂. On testing the series as triplet sensitizers for triplet–triplet annihilation upconversion, those Ir^III complexes bearing pyrenyl appendages at the 3‐ and 3,8‐positions ( Ir‐1 , Ir‐3 ) were found to give optimal upconversion quantum yields (30.2 % and 31.6 % respectively).     

Electron impact ionization of CCl4 and SF6 embedded in superfluid helium droplets

Electron impact ionization of helium nano-droplets containing several 10⁴ He atoms and doped with CCl₄ or SF₆ molecules is studied with high-mass resolution. The mass spectra show significant clustering of CCl₄ molecules, less so for SF₆ under our experimental conditions. Positive ion efficiency curves as a function of electron energy indicate complete immersion of the molecules inside the helium droplets in both cases. For CCl₄ we observe the molecular parent cation CCl₄⁺ that preferentially is formed via Penning ionization upon collisions with He*. In contrast, no parent cation SF₆⁺ is seen for He droplets doped with SF₆. The fragmentation patterns for both molecules embedded in He are compared with gas phase studies. Ionization via electron transfer to He⁺ forms highly excited ions that cannot be stabilized by the surrounding He droplet. Besides the atomic fragments F⁺ and Cl⁺ several molecular fragment cations are observed with He atoms attached.     

Relativistic molecular orbital theory of zero-field splittings in triplets

A method of calculating matrix elements of 1/r₁₂ in a basis of Dirac scattered-wave (DSW) orbitals is outlined. In the limit c → ∞, this method reduces to that described by Cook and Karplus for non-relativistic orbitals. For triplet states that can be described by a single configuration with two unpaired electrons, the relativistic exchange integrals give not only the singlet—triplet splittings (as in non-relativistic theory), but also the spin—orbit contributions to the triplet zero-field splittings. Results are reported for the ³ (n → π*) excited state of γ-thiopyrone (4H-pyran-4-thione), which has a very large value of D (calc. ?31 cm^?1, exp. ?24 to ?28 cm^?1).