Multiple photon excitation and ionization of NO in and on helium droplets

The photoexcitation of NO embedded in superfluid Hen nanodroplets having n approximately 10(4) has been examined. Two-photon excitation prepares electronically excited states (NO(*)), most notably, the embedded analog of the A 2Sigma state of gas phase NO. Vertical excitation to this low Rydberg state is blueshifted and broadened relative to its gas phase counterpart because of the repulsive electron-helium interaction. Transport to the droplet surface is believed to be facile in the superfluid. For example, NO* prefers (energetically) to reside at the droplet surface rather than at the droplet center, in contrast to NO. Photoionization of surface-bound NO* occurs over a significant photon energy range. This yields small cluster ions NO+Hek) with approximately 90% of these clusters having k< or =10. The variation of ion yield with photon energy displays a precipitous change in the region of 24 300-24 400 cm(-1) for all values of k. Possible photoionization mechanisms are discussed and it is suggested that intermediate levels with high-n Rydberg character play a role. This work underscores the important role played by transport in the photophysics of species embedded in the superfluid host.     

Triplet state dynamics in polycyclic aromatic molecules

Utilizing the technique of triplet absorption detection of magnetic resonance (TADMR), we have determined the rates of intersystem crossing for the individual spin levels of the anthracene-h₁₀ and -d₁₀ and 3,4-benzpyrene triplet states in Shpolskii solvents. The anthracene results are in agreement with other experimental and theoretical work on intersystem crossing in aromatic hydrocarbons. The benzpyrene results, however, are unique, showing a large contribution from the out-of-plane spin level. Possible explanations of this result are discussed.     

Superfluid helium droplets: a uniquely cold nanomatrix for molecules and molecular complexes

Herein, recent experiments on the spectroscopy and chemical reactions of molecules and complexes embedded in helium droplets are reviewed. In the droplets, a high spectroscopic resolution, which is comparable to the gas phase is achieved, while an isothermal low-temperature environment is maintained by evaporative cooling at T =0.37 K (4He droplets) or 0.15 K (3He droplets), lower than possible in most solid matrices. Thus the helium-droplet technique combines the benefits of both the gas phase and the classical matrix-isolation techniques. Most important, the superfluid helium facilitates binary encounters, and absorbs the released binding energy upon recombination. Thus the droplet can be viewed as an isothermal nanoscopic reactor, which isolates single molecules, clusters, or even a single reactive encounter at ultralow temperatures.     

Spectroscopic investigation of the solvation of organic molecules in superfluid helium droplets

The spectroscopy of molecules doped into superfluid helium nanodroplets provides valuable information on the process of solvation in superfluid helium. In continuation of an earlier report on emission spectra of various phthalocyanines showing a splitting of all molecular transitions in the range of about 5-12 cm(-1), the emission spectra of tetracene, pentacene, and perylene in superfluid helium droplets are presented. The new spectra and the results obtained for the phthalocyanines are explained by an empirical model which accounts for the existence of different metastable configurations of a nonsuperfluid solvation layer around the guest molecule.     

Cesium dimer spectroscopy on helium droplets

Visible absorption spectra of cesium-doped helium nanodroplets between 14,500 and 17,600 cm(-1) were probed by laser-induced fluorescence. A strong absorption band peaking around 16,700 cm(-1) is identified as Cs2 1(a) 3Sigmau+-3 3Sigmag+ transition. A broad unstructured band near 17,520 cm(-1) is assigned as the Cs2 1(X) 1Sigmag+-2 1Sigmau+ transition. Explanations of the observations are discussed on the basis of ab initio potential curves calculated by Spies and Meyer [(unpublished)]. All spectra have been modeled using narrow Frank-Condon windows around the equilibrium internuclear distance of the lowest singlet and triplet states. Many observed absorption peaks of smaller intensities could be identified, some of which may be due to transitions of cesium trimers formed on the droplets.     

High-spin alkali trimers on helium nanodroplets: spectral separation and analysis

Electronic excitation spectra of homo- (K(3),Rb(3)) and heteronuclear (K(2)Rb,KRb(2)) alkali trimers in the high-spin quartet state have been investigated in a broad spectral range (10,600-17,400 cm(-1)). Ten new bands showing laser induced fluorescence (LIF) were measured. Due to the pickup statistics, overlapping spectra of all possible oligomers are present at once, complicating the unraveling and assignment of individual spectra. To circumvent the problem, two variations of beam depletion spectroscopy were employed in addition to the conventional analysis of the relation between signal and pickup pressure: A two-laser V-type double resonance scheme combining beam depletion with LIF, and a mass selective beam depletion scheme. In principle, these allow accurate separation of an arbitrary number of overlapping spectra. The benefits and drawbacks of each method are discussed. Assignment to electronic states is achieved by comparison with ab initio complete active space self-consistent field calculations of the excited electronic level structure of the molecules.     

Triplet excitation transfer in glassy systems: spatial and spectral diffusion

Triplet excitation transfer among benzophenone molecules dissolved in glassy 2-methyltetrahydrofuran is studied by recording the emission and the optical depolarization as a function of wavelength and time. The transport mechanism is based upon exchange interaction and subject to the random character of both jump distances and site energies. Optical anisotropy data are used to gauge the probability of an excitation to remain on its original site. The anisotropy is observed to decrease by a factor of 2 from high to low energies within the inhomogeneously broadened emission band, clearly indicating hopping-mediated thermalization within the density of states. Within their excited-state lifetime the excitons do not reach the steady-state energies, but solvation allows the observation of that energy level. Unexpectedly, we find that the transfers at very short times do not contribute as much to spectral diffusion as the subsequent transport. Because the short-time hops target sites as close as approximately 1 nm, this observation suggests spatially correlated site energies for these short distances.     

Triplet state properties of pyridinium

Pyridinium phosphorescence originates at 334 nm and has a lifetime of 3.5 s; the quantum yield is roughly 0.04. The ODMR spectrum gives a zero-field splitting of |D| = 0.134 cm^?1, |E| = 0.030 cm^?1 . Implications for the lowest triplet state of pyridine are discussed.     

Comparison between positive and negative charging of helium droplets

Helium droplets of approximately 10⁴–10⁸ atoms have been produced in free jet expansions of liquid helium through a 5 μm nozzle into vacuum. The size distributions of the positively and negatively charged droplets were measured as a function of the electron emission current. A simple model has been developed to describe the charging process and formulas for production of singly and doubly charged droplets were derived. The ratio of the ionization cross section to the geometrical cross section and its dependence on N was obtained. In the experiment single negatively and positively charged droplets were observed. Only for sizes N larger than a certain threshold size N _th ≈ 2 × 10⁵ the positively charged droplets were found to be doubly ionized. These observations are in good agreement with the assumption, that the positively charge carriers are stable “snowballs” while the negative droplets contain an excess electron located in the inside within a metastably bound “bubble”. The threshold size N _th corresponds to a simple model in which for smaller droplets a positively charged cluster of about 50 atoms is ejected.     

Quantum solvation of phthalocyanine in superfluid helium droplets

We have measured quantum states of the solvent-solute system of phthalocyanine in superfluid helium droplets in a high resolution pump-probe experiment. This provides evidence for the attribution of a splitting effect in the emission spectra of phthalocyanine in helium droplets to the relaxation of the first helium layer upon electronic excitation, measured recently by us. Our experimental results are a strong indication for the first helium layer playing a key roll for the solvation of molecules in helium droplets and, thus, for their spectroscopic features.     

Microsolvation of phthalocyanines in superfluid helium droplets.

Experimental and theoretical investigations of the spectroscopy of molecules in superfluid helium droplets provide evidence for the key role of the first helium layer surrounding the dopant molecule in determining the molecule's spectroscopic features. Recent investigations of emission spectra of phthalocyanine in helium droplets revealed a doubling of all transitions. Herein, we present the emission spectra of Mg-phthalocyanine and of phthalocyanine-argon clusters in helium droplets, which confirm the splitting as a general effect of the helium environment. A scheme of levels is deduced from the emission spectra and attributed to quantized states of the first helium layer surrounding the dopant molecule.     

Triplet state dipole moments of aminobenzonitriles

The triplet state dipole moments mu(T) of a series of 4-amino- and 3-aminobenzonitriles in cyclohexane, benzene, and 1,4-dioxane are recalculated from previously published [J. Phys. Chem. 1992, 96, 10809] time-resolved microwave conductivity data, on the basis of newly measured intersystem crossing yields. For 4-(dimethylamino)benzonitrile (DMABN), the following values are now determined for mu(T): 8.3 D (cyclohexane), 8.9 D (benzene), and 9.7 D (1,4-dioxane), as compared with the previously reported dipole moment of 12 D for the first and the last solvent. With the other aminobenzonitriles, similar mu(T) data are obtained, between 6.9 D for 4-aminobenzonitrile (ABN) in n-hexane and 10.0 D for 4-(di-n-decylamino)benzonitrile (DDABN) in 1,4-dioxane. The increase of mu(T) observed for all aminobenzonitriles when going from cyclohexane via benzene to 1,4-dioxane may indicate that their triplet dipole moments become larger with increasing solvent polarity. The present mu(T) of DMABN, between 8.3 and 9.7 D, although larger than the ground state dipole moment mu(0) of 6.6 D, is somewhat smaller than that of the locally excited (LE) state (9.9 D) but considerably smaller than the dipole moment of the intramolecular charge transfer (ICT) state (17 D). By comparing these mu(X) data with the frequency (CN) of the cyano vibration in each state, it appears that at least for DMABN in the triplet state (CN) is not a reliable indication of the extent of charge transfer as compared with the other states S0, LE, and ICT.     

Laser-assisted electron-impact excitation of hydrogen and helium atoms

The excitation of H(1s–2s) and He(1¹ S–2¹ S) by electron impact in the presence of a nonresonant laser field is studied in the framework of the perturbation theory. The wavelength variation of the total cross section is presented at incident electron energies of 100 eV and 200 eV for hydrogen and 200 eV for helium. The use of pseudostates as intermediate states in the study of excitation of hydrogen is also investigated.     

Formation and properties of metal clusters isolated in helium droplets

The unique conditions forming atomic and molecular complexes and clusters using superfluid helium nanodroplets have opened up an innovative route for studying the physical and chemical properties of matter on the nanoscale. This review summarizes the specific characteristics of the formation of atomic clusters partly generated far from equilibrium in the helium environment. Special emphasis is on the optical response, electronic properties as well as dynamical processes which are mostly affected by the surrounding quantum matrix. Experiments include the optical induced response of isolated cluster systems in helium under quite different excitation conditions ranging from the linear regime up to the violent interaction with a strong laser field leading to Coulomb explosion and the generation of highly charged atomic fragments. The variety of results on the outstanding properties in the quantum size regime highlights the peculiar capabilities of helium nanodroplet isolation spectroscopy.     

Photoelectron studies of neutral Ag3 in helium droplets

Photoelectron spectra of neutral silver trimers, grown in ultracold helium nanodroplets, are recorded after ionization with laser pulses via a strong optical resonance of this species. Varying the photon energy reveals that direct vertical two-photon ionization is hindered by a rapid relaxation into the lower edge of a long-living excited state manifold. An analysis of the ionization threshold of the embedded trimer yields an ionization potential of 5.74+/-0.09 eV consistent with the value found in the gas phase. The asymmetrical form of the electron energy spectrum, which is broadened toward lower kinetic energies, is attributed to the influence of the matrix on the photoionization process. The lifetime of the excited state was measured in a two-color pump-probe experiment to be 5.7+/-0.6 ns.     

Electron interaction with nitromethane embedded in helium droplets: attachment and ionization measurements

Results of a detailed study on electron interactions with nitromethane (CH(3)NO(2)) embedded in helium nanodroplets are reported. Anionic and cationic products formed are analysed by mass spectrometry. When the doped helium droplets are irradiated with low-energy electrons of about 2 eV kinetic energy, exclusively parent cluster anions (CH(3)NO(2))(n)(-) are formed. At 8.5 eV, three anion cluster series are observed, i.e., (CH(3)NO(2))(n)(-), [(CH(3)NO(2))(n)-H](-), and (CH(3)NO(2))(n)NO(2)(-), the latter being the most abundant. The results obtained for anions are compared with previous electron attachment studies with bare nitromethane and nitromethane condensed on a surface. The cation chemistry (induced by electron ionization of the helium matrix at 70 eV and subsequent charge transfer from He(+) to the dopant cluster) is dominated by production of methylated and protonated nitromethane clusters, (CH(3)NO(2))(n)CH(3)(+) and (CH(3)NO(2))(n)H(+).     

Hydrogen recombination on metals: vibrational excitation of desorbed molecules

The vibrational excitation of hydrogen molecules formed by recombination of hydrogen atoms on different metal surfaces has been studied. A recently developed experimental technique was used to determine vibrational state populations of the molecules up to v=7. Excitation of high vibrational levels is observed for molecules formed on metal surfaces which strongly chemisorb hydrogen. Metals with weaker chemisorption lead to vibrational excitation of lower levels, predominantly up to v=3. Knowledge of the vibrational state of desorbed molecules gives information on the energy of adsorbed hydrogen atoms and on the dynamics of surface reactions. This information is complementary to that obtained from studies of hydrogen reactions with metal clusters.     

Photoelectron imaging of helium droplets doped with Xe and Kr atoms

Helium droplets doped with Xe and Kr atoms were photoionized by using VUV synchrotron radiation from the Advanced Light Source and the resulting photoelectron images were measured. A wide range of He droplet sizes, photon energies, and dopant pick-up conditions was investigated. Significant ionization of dopants was observed at 21.6 eV, the absorption maximum of 2p (1)P1 electronic excited state of He droplets, indicating an indirect ionization mechanism via excitation transfer. The photoelectron images and spectra reveal multiple photoionization mechanisms and pathways for the photoelectrons to escape the droplet. Specifically, they show sets of sharp peaks assigned to two mechanisms for Penning ionization of the dopant by He* in which the photoelectrons leave the droplet with no detectable energy loss, a broad, intense feature representing electrons that undergo significant energy loss, and a small amount of ultraslow electrons that may result from electron trapping at the droplet surface. The droplet-size dependence of the broad, intense feature suggests the development of the conduction band edge in the largest droplets seen here ((N) approximately 250,000).     

Membrane distillation: theory and experiments

A theoretical approach is presented that describes membrane distillation processes due to the simultaneous action (in a proactive or in a counteractive way) of temperature and concentration differences through porous hydrophobic membranes. The model developed emphasizes the importance of the boundary layers, shows the existence of a coupling term between the two thermodynamic forces acting on the system, and permits the definition and characterization of the so-called steady states. In order to check the model, two membranes have been studied in different experimental conditions. The influence of some relevant parameters, such as solution concentration, stirring rate, mean temperature and temperature difference has been considered and the theoretical predictions of the model have been applied to the obtained results. The accordance may be considered good.