N-H...pi interactions in pyrroles: systematic trends from the vibrational spectroscopy of clusters

Pyrrole and some of its methylated derivatives are aggregated in a controlled way in pulsed supersonic jet expansions. The cluster N-H stretching dynamics is studied using FTIR and Raman spectroscopy. Dimers, trimers and tetramers can be differentiated. Systematic trends in the dimer N-H...pi interaction as a function of methyl substitution are identified and explored for predictions. Overtone jet absorption spectroscopy is used to extract anharmonicities for the N-H bond in different environments. The N-H anharmonicity constant increases by 10% upon dimerization. Bulk matrix shifts can be emulated by the formation of Ar-decorated clusters. The experimental results are expected to serve as benchmarks for an accurate ab initio characterization of the N-H...pi hydrogen bond.     

Hydrogen-bonded OH stretching modes of methanol clusters: a combined IR and Raman isotopomer study

A comprehensive study of the OH and OD stretching fundamentals in clusters of methanol and its isotopomers CH(3)OD, CD(3)OH, and CD(3)OD provides detailed insights into the hydrogen-bond mediated coupling as a function of cluster size. The combination of infrared and Raman supersonic jet spectroscopy enables the observation and assignment of all hydrogen-bonded OH stretching modes of isolated methanol trimer and methanol tetramer. A consistent explanation for the spectral complexity observed more than a decade ago in methanol trimer in terms of low-frequency methyl umbrella motions is provided. Previous explanations based on cluster isomerism or anharmonic resonances are ruled out by dedicated jet experiments. The first experimental lower bound for concerted quadruple proton transfer in S(4) symmetric methanol tetramer is derived and compared with theoretical predictions. The observed isotope effects offer insights into the anharmonicity of the localized OH bond. The performance of harmonic B3LYP and MP2 calculations in predicting hydrogen-bond-induced spectral shifts and couplings is investigated.     

Spectroscopic characterization of N(2)O aggregates: from clusters to the particulate state

Collisional cooling is used to generate N(2)O particles with radii ranging from the subnanometer to the submicrometer region. The vibrational dynamics of the aggregates is studied by Fourier transform infrared spectroscopy. In the region of the stretching fundamentals and combination bands, the infrared spectra of the particles exhibit characteristic size-dependent features. For the very small particles, the results obtained from collisional cooling are compared for the first time with corresponding results from supersonic jet expansions. It turns out that with both methods very similar clusters are generated. A pronounced temperature dependence of a combination band maximum in the collisional cooling cell spectra is found. This correlation is exploited to estimate cluster temperatures in supersonic jet spectra.     

Diffraction and vibrational dynamics of large clusters from He atom scattering

The vibrational dynamics of large Ar _n clusters from n=30 to n=4500 is investigated by measuring the energy loss of He atoms in a high resolution scattering experiment. The clusters are generated by adiabatic expansion through conical nozzles and contain a distribution of cluster sizes. The He supersonic nozzle beam provides a resolution of better than 1 meV. The results are compared with calculated spectral density functions for single cluster sizes and bulk phonon spectra.     

Supersonic jet spectroscopy of naphthalene–fluorene bichromophoric cluster

We have investigated the supersonic jet spectroscopy and photophysics of 1-methylnaphthalene–fluorene (1MN–FL) cluster, and looked for indications of intramolecular electronic energy transfer (Intra-EET) from the FL (donor, D) to 1MN (acceptor, A). The clusters were identified by their time of flight (TOF) mass spectra. We observed clusters bands in the LIF spectrum near the region of 1MN origin. We have also observed cluster TOF–resonance enhanced multi-photon ionization (REMPI) spectrum near the electronic origin of the fluorene moiety. However, this spectrum was almost independent of the excitation wavelength, and was not observed in the LIF spectrum. This is probably due to fast Intra-EET resulting in lifetime broadening of the donor chromophore cluster spectrum, similar to that observed previously for the naphthalene–anthracene bichromophoric system.     

IR spectroscopy on isolated Co(n)(alcohol)m cluster anions (n=1-4, m=1-3): structures and spin states

Isolated cobalt-alcohol cluster anions containing n=1-4 cobalt and m=1-3 alcohol molecules (alcohol=methanol, ethanol, propanol) are produced in a supersonic beam by using a laser ablation source. By applying IR photodissociation spectroscopy vibrational spectra in the OH stretching region are obtained. Several structures in different spin states are discussed for the (n,m) clusters. In comparison with density functional theory calculations applied to both the Co/alcohol clusters and the naked Co cluster anions, an unambiguous structural assignment is achieved. It turns out that structures are preferred with a maximum number of hydrogen bonds between the OH groups and the Co···Co units. These hydrogen bonds are typical for anionic species leading to an activation of the OH groups which is indicated by large red-shifts of the OH stretching frequencies compared to the naked alcohols. For each (n,m) cluster, the frequency shifts systematically with respect to the different alcohols, but the type of structure is identical for all alcohol ligands. The application of IR spectroscopy turns out to be an ideal tool not only as a probe for structures but also for spin states which significantly influence the predicted OH stretching frequencies.     

Infrared spectra of helium clusters seeded with nitrous oxide, 4HeN-N2O, with N=1-80

High resolution infrared spectra of HeN-N2O clusters are studied in the 2200 cm(-1) region of the N2O nu1 fundamental band. The clusters are produced in a pulsed supersonic jet expansion from a cooled nozzle source and probed using a tunable diode laser operating in a rapid-scan mode. Three isotopic forms are used (14N14N16O, 15N14N16O, and 15N15N16O) in order to support the spectral analyses. For clusters up to N approximately 24, the individual spectra are resolved, assigned, and analyzed together with complementary microwave data. Assignments for larger clusters are uncertain due to overlapping transitions, but an approximate analysis is still possible for N approximately 25-80. Compared to helium clusters containing the related CO2 or OCS molecules, the rotational dynamics of HeN-N2O clusters show similarities but also important differences. In particular, HeN-N2O has more irregular behavior in the range of N=6-17, indicating that conventional molecular structure plays a greater role. In general terms, these differences can be attributed to a greater degree of angular anisotropy in the He-N2O intermolecular potential.     

An indigenous cluster beam apparatus with a reflectron time-of-flight mass spectrometer

The design and fabrication of a Smalley-type cluster source in combination with a reflectron based time-of-flight (TOF) mass spectrometer are reported. The generation of clusters is based on supersonic jet expansion of the sampling plume. Sample cells for both liquid and solid targets developed for this purpose are described. Two pulsed Nd-YAG lasers are used in tandem, one (532 nm) for target vapourization and the other (355 nm) for cluster ionization. Methanol clusters of nuclearity up to 14 (mass 500 amu) were produced from liquid methanol as the test sample. The clusters were detected with a mass resolution of ∼ 2500 in the R-TOF geometry. Carbon clusters up to a nuclearity of 28 were obtained using a polyimide target. The utility of the instrument is demonstrated by carrying out experiments to generate mixed clusters from alcohol mixtures.     

Infrared and ab initio studies on 1,2,4,5-tetrafluorobenzene clusters with methanol and 2,2,2-trifluoroethanol: presence and absence of an aromatic C-H...O hydrogen bond

The (1:1) clusters of 1,2,4,5-tetrafluorobenzene (TFB) with methanol and with 2,2,2-trifluoroethanol (TFE) were studied both experimentally and computationally. Through use of fluorescence-detected infrared spectroscopy, the (1:1) clusters were identified in supersonic jets. Intermolecular interactions in the clusters were characterized by the spectral shifts of the aromatic C-H stretching modes in the TFB moiety owing to the cluster formation. The molecular structures, stabilization energies, and vibrational frequencies of the clusters were computed at the MP2/6-31+G level. Both computational and experimental data indicate that an aromatic C-H...O hydrogen bond is present in the TFB-methanol cluster, while it is absent in the TFB-TFE cluster.     

On the zirconium oxide neutral cluster distribution in the gas phase: detection through 118 nm single photon, and 193 and 355 nm multiphoton, ionization

Zirconium oxide clusters are generated in the gas phase by laser ablation of the metal into a flow of ca. 5% O2/95% He at 100 psig and supersonic expansion into a vacuum chamber. Mass spectra of neutral gas phase zirconium oxide clusters are obtained through photoionization at three different laser wavelengths: 118, 193, and 355 nm. Ionization of the clusters with 118 nm laser radiation is through a single photon ionization mechanism, while ionization by 193 and 355 nm laser radiation is through a multiphoton (three or more photon) mechanism. Fragment ion features are observed in the mass spectra of ZrmOn+ for only the 193 nm and 355 nm ionization schemes. The true neutral ZrmOn cluster distribution is obtained only through 118 nm single photon ionization, as verified by mass spectral peak linewidths and calculations of the cluster binding energies, ionization energies, and fragmentation rates. The neutral cluster distribution consists mainly of the series ZrmO2m and ZrmO(2m+1) for m = 1,..., approximately 30.     

Size-selected infrared predissociation spectroscopy of neutral and cationic formamide-water clusters: stepwise growth of hydrated structures and intracluster hydrogen transfer induced by vacuum-ultraviolet photoionization

Vibrational spectroscopy of size-selected formamide-water clusters, FA-(H2O)n , n = 1-4, prepared in a supersonic jet is performed with vacuum-ultraviolet-ionization detected-infrared predissociation spectroscopy (VUV-ID-IRPDS). The cluster structures are determined through comparisons of the observed IR spectra with theoretical calculations at the MP2/6-31++G** level. The FA-(H2O)n , n = 1-3, clusters have ring-type structures, where water molecules act as both single donor and single acceptor in the hydrogen-bond network between the amino and carbonyl groups of FA. For FA-(H2O)4, on the other hand, the absence of the free NH stretching vibration indicates formation of a double ring type structure, where two NH bonds of the amino group and the carbonyl oxygen of FA form hydrogen bonds with water molecules. An infrared spectrum of the formamide-water cluster cation, [FA-H2O](+), is also observed with infrared predissociation spectroscopy of vacuum-ultraviolet-pumped ion (IRPDS-VUV-PI). No band is observed for the free OH stretches of neutral water. This shows [FA-H2O](+) has such a structure that one of the hydrogen atoms of the water moiety is transferred to the carbonyl oxygen of FA(+).     

Hydrogen-bonded structures for self-aggregates of 2,5-dimethylpyrrole and its binary clusters with pyrrole studied by IR cavity ringdown spectroscopy

N-H···π hydrogen-bonded (H-bonded) structures were studied by applying vibrational spectroscopy to self-aggregate clusters of 2,5-dimethylpyrrole (DMPy) and its binary clusters with pyrrole (Py). The NH stretching vibrations of jet-cooled clusters were observed by IR cavity ringdown spectroscopy. A combination of experiments and density functional theory calculations revealed the stable structures, intermolecular binding energies, and harmonic vibrational frequencies. The IR spectrum of the DMPy self-aggregate clusters was very similar in spectral features to that of the Py clusters in a previous work. The observed NH stretching vibrations at 3505, 3420, 3371, and 3353 cm(-1) are simultaneously red-shifted by ～25 cm(-1) from the Py monomer, dimer, trimer, and tetramer, respectively. Based on a spectral analogy of DMPy with Py, and a consistency of the calculated harmonic frequencies with experiments, the H-bonded structures of the DMPy clusters were determined to be of a T-shape for a dimer and a cyclic for a trimer and a tetramer. For the DMPy-Py binary clusters, we discussed the stability and geometry of the N-H···π interactions in the T-shaped dimer and the cyclic trimer. The binary dimer showed the only single NH stretch at 3419 cm(-1) in the IR spectrum. A vibrational analysis of the H-bonded NH stretches as well as the calculated stabilization energies deduced that only the binary dimer by DMPy as an acceptor and Py as a donor can exist in a supersonic jet. For binary trimers, NH stretches were observed due to both (DMPy)(2)-(Py)(1) and (DMPy)(1)-(Py)(2). They were found to have different vibrational patterns from each other; the former showed three dispersed NH stretches, and the other had two quasi-degenerate NH stretches. Throughout this study, we also considered the intermolecular geometries, such as the H-bond distance and the angle in terms of the methyl group substitution effect.     

Gold cluster carbonyls: vibrational spectroscopy of the anions and the effects of cluster size, charge, and coverage on the CO stretching frequency

We report the vibrational spectra of the carbonyl complexes of anionic gold clusters in the range of the CO stretching frequency as measured in the gas phase using IR multiple photon dissociation spectroscopy. The investigated complexes contain between 3 and 14 Au atoms and up to 7 CO ligands. Special attention is given to the complexes that exhibit saturation CO coverage as well as to the monocarbonyl species. In conjunction with data from the corresponding cationic complexes we quantify how the CO stretching frequency varies with the charge state of the gold cluster. Our results provide a size- and charge-dependent basis to interpret values of the CO stretching frequency measured for CO on deposited gold clusters in terms of the charge states of the clusters.     

Spectra of the liquid cluster surface thermal fluctuations

Classification of cluster particles is proposed that introduces three particle types: the internal particles, surface particles, and virtual chains of particles. Thermal fluctuations of a surface passing through the surface particles of a Lennard-Jones liquid cluster are studied using a molecular dynamics simulation. It is shown that for large clusters, the Fourier spectral amplitude of these fluctuations decays faster than 1q, where q is the wave number. The frequency Fourier spectrum shows an overdamped system behavior, which is the evidence for the absence of thermal capillary waves for clusters comprising less than 10(5) particles. The time-averaged cluster density profile is given by an error function with the width parameter diverging as the logarithm of the cluster size.     

Helium clusters seeded with CO molecules: new results for HeN-13C18O and the approach to the nanodroplet limit

Infrared spectra of helium clusters seeded with doubly substituted carbon monoxide molecules, 13C18O, have been studied in order to complement recent helium nanocluster results and to determine whether additional isotopic data would help to separate vibrational and rotational contributions to the observed transitions. The experiments were made by direct infrared absorption in pulsed supersonic jet expansions using a tunable diode laser probe in the region of the fundamental band (approximately 2045 cm-1 for 13C18O). Even with data on the R0 transitions from four CO isotopomers, it was found that a clear and consistent separation of vibration and rotation could not be achieved for HeN-CO clusters in the size range N approximately 10-20. Isotope shifts observed for clusters with 13C18O (relative to 12C16O) were found to be close to the sums of the shifts previously determined for 13C16O and 12C18O. The new measurements generally supported previous assignments of cluster size, but some modifications for the range N=14-16 are suggested here. New measurements for HeN-12C16O under conditions favoring larger clusters (high backing pressure and low jet temperature) showed that individual transitions could be resolved even at N approximately 50. For larger clusters, a partly resolved "lump" of transitions was observed to approach the nanodroplet limit.     

Surface induced reactions of cluster ions

First results are presented from a new apparatus, consisting of a supersonic beam for generating neutral clusters, a variable energy electron gun for ionizing the clusters, and a tandem mass spectrometer set-up for studying surface induced reactions of mass and energy selected cluster ions. Rare gas cluster ions, fragment ions from SF₆, benzene ions and benzene cluster ions have been investigated so far. Cluster ion dissociation, intracluster ion molecule reactions and surface reactions with adsorbed hydrocarbons have been shown to be important reaction channels for these ion-surface collision at energies ranging from a few eV to 500 eV. The surface induced fragmentation spectrum is demonstrated to be a useful tool for probing binding energy and structure of cluster ions.     

NH stretching vibrations of pyrrole clusters studied by infrared cavity ringdown spectroscopy

The IR spectra for various sizes of pyrrole clusters were measured in the NH stretching vibration region by infrared cavity ringdown spectroscopy. The hydrogen-bonded structures and normal modes of the pyrrole clusters were analyzed by a density functional theory calculation of the B3LYP/6-311+G(d,p) level. Two types of pulsed nozzles, a slit and a large pinhole, were used to generate different cluster size distributions in a supersonic jet. A rotational contour analysis of the NH stretching vibration for the monomer revealed that the slit nozzle provides a warmer jet condition than the pinhole one. The IR spectra, measured under the warmer condition, showed the intense bands at 3444, 3392, and 3382 cm(-1), which were assigned to hydrogen-bonded NH stretching vibrations due to the dimer, the trimer, and the tetramer, respectively. On the other hand, the IR spectra measured under a lower temperature condition by a pinhole nozzle showed a broad absorption feature in addition to sharp bands. This broad absorption was reproduced by the sum of two Gaussians peaks at 3400 and 3372 cm(-1) with widths of 30 and 50 cm(-1) (FWHM), respectively. Compared with the spectra of the condensed phase, two bands at 3400 and 3372 cm(-1) were assigned to hydrogen-bonded NH stretching vibrations of larger clusters having liquid-like and solid-like structures, respectively.     

A supersonic beam ion cyclotron resonance instrument for the study of van der Waals cluster ions

For the study of ionized van der Waals cluster ions an instrument is presented, which consists of a supersonic beam cluster source coupled to an ICR spectrometer with external ion source. The neutral van der Waals clusters are generated by supersonic expansion and ionized by electron impact in the external source. The cluster ions are extracted at right angle to the neutral cluster beam and fly collision-free parallel to the magnetic field direction into the differentially pumped ICR cell. For the ion transfer, an improved lens system is presented. The cluster ion transfer lens system is capable of focusing ions with energies of a few eV perpendicular to the magnetic field direction through the differential pumping orifice. The ions are injected into the ICR cell with a trap barrier pulse, ion accumulation is possible. With this system the first ICR spectra of small cluster ions of carbon dioxide are obtained.     

Elementary peptide motifs in the gas phase: FTIR aggregation study of formamide, acetamide, N-methylformamide, and N-methylacetamide

Cold, isolated peptide model compounds and their aggregates are generated in pulsed supersonic jet expansions and detected by FTIR spectroscopy in the amide-A region, complemented by amide-I spectra. The most stable, symmetric dimer of formamide is unambiguously assigned in the gas phase for the first time, also by comparison to the analogous acetamide dimer. Efficient quenching of a hot-state Fermi resonance by cooling of the dimers is invoked. As the preferred relative orientation of the C=O and N-H groups in N-methylated formamide and acetamide is trans, these compounds show a fundamentally different dimerization pattern. Their most stable dimers, which would be analogous to those of formamide and acetamide, remain undetected as a consequence of kinetic control in the jet. Accurate benchmark quantities for multidimensional vibrational treatments of these peptide models are derived, and the influence of methyl groups on the N-H stretching dynamics is discussed.     

Size-selected methyl lactate clusters: fragmentation and spectroscopic fingerprints of chiral recognition

A comprehensive experimental study of the OH stretching vibrations of size-selected clusters of enantiopure and racemic methyl lactate is presented. For the size selection, we measured angular dependent mass spectra and time-of-flight distributions at the different fragment masses. In this way the fragmentation of these clusters upon electron impact ionization is obtained. The largest fragment masses of the neutral (MLac)n clusters are the protonated (MLac)n-1H+ ions. The results of a pressure dependent study in an FTIR jet experiment are compared with completely size-selected experiments based on atomic beam deflection and depletion spectroscopy. The size assignments and spectra agree for dimers and trimers. Structures and spectral information for the trimer and the tetramer at density functional and MP2 level are provided. Selective self-aggregation and chiral recognition was observed for homochiral trimers. They exhibit a ring structure bound by OH...OH hydrogen bonds. A spectacular switch in the hydrogen bonding topology was observed for the tetramer. The homochiral enantiomer exhibits cooperative OH...OH bonding, while the heterochiral version shows isolated OH...O=C bonding in a symmetric SRSR arrangement. The crucial ingredients for this identification are the size-selective IR spectra with their different shifts and line patterns which are reproduced by the calculations.