Physics

Spectra of ethylene dimers and trimers are studied in the nu11 and (for the dimer) nu9 fundamental band regions of C2H4 (~2990 and 3100 cm-1) using a tunable optical parametric oscillator source to probe a pulsed supersonic slit jet expansion. The deuterated trimer has been observed previously, but this represents the first rotationally resolved spectrum of (C2H4)3. The results support the previously determined cross-shaped (D2d) dimer and barrel-shaped (C3h or C3) trimer structures. However, the dimer spectrum in the nu9 fundamental region of C2H4 is apparently very perturbed and a previous rotational analysis is not well verified.

Infrared spectra of Rg1,2 - C6H6 complexes (Rg = He, Ne, Ar) are observed in the region of the nu12 fundamental of C6H6 using a pulsed supersonic jet expansion and a tunable optical parametric oscillator laser source. The mixed trimer He - Ne - C6H6 is also detected. Four bands are analyzed for each complex, namely nu12 itself (~3048 cm-1) and three linked combination bands (~3079, 3100, and 3102 cm-1). The results are consistent with previous ultraviolet and microwave results, with Ne2 - C6H6 and He - Ne - C6H6 being analyzed spectroscopically here for the first time.

Only a few weakly-bound complexes containing the O2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added by the oxygen molecule's unpaired electron spin. Here we report an extensive infrared spectrum of CO-O2, observed in the CO fundamental band region using a tunable quantum cascade laser to probe a pulsed supersonic jet expansion. The rotational energy level pattern derived from the spectrum consists of stacks of levels characterized by the total angular momentum, J, and its projection on the intermolecular axis, K. Five such stacks are observed in the ground vibrational state, and ten in the excited state (v(CO) = 1). They are divided into two groups, with no observed transitions between groups. The groups correspond to different projections of the O2 electron spin, and correlate with the two lowest rotational states of O2, (N, J) = (1, 0) and (1, 2). The rotational constant of the lowest K = 0 stack implies an effective intermolecular separation of 3.82 Angstroms, but this should be interpreted with caution since it ignores possible effects of electron spin. A new high-level 4-dimensional potential energy surface is developed for CO-O2, and rotational energy levels are calculated for this surface, ignoring electron spin. By comparing calculated and observed levels, it is possible to assign detailed quantum labels to the observed level stacks.

High order harmonic generation from clusters is a controversial topic: conflicting theories exist, with different explanations for similar experimental observations. From an experimental point of view, separating the contributions from monomers and clusters is challenging. By performing a spectrally and spatially resolved study in a controlled mixture of clusters and monomers, we are able to isolate a region of the spectrum where the emission purely originates from clusters. Surpringly, the emission from clusters is depolarized, which is the signature of statistical inhomogeneous emission from a low-density source. The harmonic response to laser ellipticity shows that this generation is produced by a new recollisional mechanism, which opens the way to future theoretical studies.

The use of inorganic crystals technology has been widely date. Since quartz crystals for watches in the nineteenth century, and common way radio in the early twentieth century, to computer chips with new semiconductor materials. Chemical elements such as beryllium, lithium, selenium and silicon, are widely used in technology. The development of new crystals arising from that arrangement can bring technological advances in several areas of knowledge. The likely difficulty of finding such crystals in nature or synthesized, suggest an advanced study of the subject. A study using computer programs with ab initio method was applied. As a result of the likely molecular structure of the arrangement of a crystal was obtained.

In this review, we discuss the use of time-of-flight secondary-ion mass spectrometry (TOF-SIMS) technology for analyzing the viscous glue (is called aggregate glue droplets) of spider orb webs and examine the results obtained. Element distribution images of the aggregate glue droplets were observed by TOF-SIMS. A uniform element distribution is seen for suspended pristine aggregate glue droplets, and a differential spreading of aggregate glue components is seen for attached aggregate glue droplets. We also observed TOF-SIMS images of water in aggregate glue droplets, where water was observed to be consistent with the distribution of oozing salt. We also found that the alkali metal in the aggregate glue droplets showed similar characteristics by feeding cesium carbonate to spiders.

Interatomic Coulombic decay (ICD) is induced in helium (He) nanodroplets by photoexciting the n=2 excited state of He^+ using XUV synchrotron radiation. By recording multiple coincidence electron and ion images we find that ICD occurs in various locations at the droplet surface, inside the surface region, or in the droplet interior. ICD at the surface gives rise to energetic He^+ ions as previously observed for free He dimers. ICD deeper inside leads to the ejection of slow He^+ ions due to Coulomb explosion delayed by elastic collisions with neighboring He atoms, and to the formation of He_k^+ complexes.

We investigate the onset of photoionization shakeup induced interatomic Coulombic decay (ICD) in He2 at the He+*(n = 2) threshold by detecting two He+ ions in coincidence. We find this threshold to be shifted towards higher energies compared to the same threshold in the monomer. The shifted onset of ion pairs created by ICD is attributed to a recapture of the threshold photoelectron after the emission of the faster ICD electron.

Infrared combination bands of the polar isomer of the N2O dimer are observed for the first time, using a tunable infrared laser source to probe a pulsed slit-jet supersonic expansion in the N2O nu1 region (~2240 cm-1). One band involves the torsional (out-of-plane) intermolecular mode and yields a torsional frequency of 19.83 cm-1 if associated with the out-of-phase fundamental (N2O nu1) vibration of the N2O monomers in the dimer. The other band, which is highly perturbed, yields an intermolecular in-plane geared bend frequency of 22.74 cm-1. The results are compared with high level ab initio calculations. The less likely alternate assignment to the in-phase fundamental would give torsional and geared bend frequencies of 17.25 and 20.16 cm-1, respectively.

We have calculated partial contributions of different endohedral and atomic subshells to the total dipole sum rule in the frame of the random phase approximation with exchange (RPAE) and found that they are essentially different from the numbers of electrons in respective subshells. This difference manifests the strength of the intershell interaction. We present concrete results of calculations for endohedrals, composed of fullerene C60 and all noble gases He, Ne, Ar, Kr and Xe thus forming respectively He@C60, Ne@C60, Ar@C60, Kr@C60, and Xe@C60. For comparison we obtained similar results for isolated noble gas atoms. The deviation from number of electrons in outer subshells proved to be much bigger in endohedrals than in isolated atoms thus demonstrating considerably stronger intershell correlations there.