Molecular supersonic beam

As with most methods for studying ion-molecule kinetics and dynamics, numerous variations exist. For low-energy processes, the collision cell can be replaced with a molecular beam perpendicular to the ion beam [106]. This greatly reduces the thennal energy spread of the reactant neutral. Another approach for low energies is to use a merged beam [103]. In this system the supersonic expansion is aimed at the tluoat of the octopole, and the ions are passed tluough... 

Several instniments have been developed for measuring kinetics at temperatures below that of liquid nitrogen [81]. Liquid helium cooled drift tubes and ion traps have been employed, but this apparatus is of limited use since most gases freeze at temperatures below about 80 K. Molecules can be maintained in the gas phase at low temperatures in a free jet expansion. The CRESU apparatus (acronym for the French translation of reaction kinetics at supersonic conditions) uses a Laval nozzle expansion to obtain temperatures of 8-160 K. The merged ion beam and molecular beam apparatus are described above. These teclmiques have provided important infonnation on reactions pertinent to interstellar-cloud chemistry as well as the temperature dependence of reactions in a regime not otherwise accessible. In particular, infonnation on ion-molecule collision rates as a ftmction of temperature has proven valuable m refining theoretical calculations. 

The fonnation of clusters in the gas phase involves condensation of the vapour of the constituents, with the exception of the electrospray source [6], where ion-solvent clusters are produced directly from a liquid solution. For rare gas or molecular clusters, supersonic beams are used to initiate cluster fonnation. For nonvolatile materials, the vapours can be produced in one of several ways including laser vaporization, thennal evaporation and sputtering. 

New to the fourth edition are the topics of laser detection and ranging (LIDAR), cavity ring-down spectroscopy, femtosecond lasers and femtosecond spectroscopy, and the use of laser-induced fluorescence excitation for stmctural investigations of much larger molecules than had been possible previously. This latter technique takes advantage of two experimental quantum leaps the development of very high resolution lasers in the visible and ultraviolet regions and of the supersonic molecular beam. 

Beam Spectroscopy. Both specificity and sensitivity can be gready enhanced by suppressing coUisional and Doppler broadening. This is accompHshed in supersonic atomic and molecular beams (296) by probing the beam transversely to its direction of dow in a near-coUisionless regime. 

We have so far assumed that the atoms deposited from the vapor phase or from dilute solution strike randomly and balHstically on the crystal surface. However, the material to be crystallized would normally be transported through another medium. Even if this is achieved by hydrodynamic convection, it must nevertheless overcome the last displacement for incorporation by a random diffusion process. Therefore, diffusion of material (as well as of heat) is the most important transport mechanism during crystal growth. An exception, to some extent, is molecular beam epitaxy (MBE) (see [3,12-14] and [15-19]) where the atoms may arrive non-thermalized at supersonic speeds on the crystal surface. But again, after their deposition, surface diffusion then comes into play. 

The spectrometer is fitted with a skimmed c.w. supersonic molecular beam source. Many chiral species of interest are of low volatility, so a heated nozzle-reservoir assembly is used to generate, in a small chamber behind a 70-pm pinhole, a sample vapor pressure that is then seeded in a He carrier gas as it expands through the nozzle [103], Further details of this apparatus are given elsewhere [36, 102, 104],... 

There are at least three approaches to fast GC/MS (1) use of microbore columns with time-of-flight mass spectrometry (TOFMS) (2) use of low-pressure (LP)-GC/MS to aid separations at increased flow rate " and (3) use of supersonic molecular beam mass spectrometry (SMBMS) (also known as supersonic GC/MS), which can accept increased flow rates and short analytical columns."... 

Supersonic molecular beam (SMB) mass spectrometry (SMB-MS) measures the mass spectrum of vibra-tionally cold molecules (cold El). Supersonic molecular beams [43] are formed by the co-expansion of an atmospheric pressure helium or hydrogen carrier gas, seeded with heavier sample organic molecules, through a simple pinhole (ca. 100 p,m i.d.) into a 10 5-mbar vacuum with flow-rates of 200 ml. rn in. In SMB, molecular ionisation is obtained either through improved electron impact ionisation, or through hyperthermal surface ionisation... 

Enhanced molecular ion implies reduced matrix interference. An SMB-El mass spectrum usually provides information comparable to field ionisation, but fragmentation can be promoted through increase of the electron energy. For many compounds the sensitivity of HSI can be up to 100 times that of El. Aromatics are ionised with a much greater efficiency than saturated compounds. Supersonic molecular beams are used in mass spectrometry in conjunction with GC-MS [44], LC-MS [45] and laser-induced multiphoton ionisation followed by time-of-flight analysis [46]. 

Syage JA, Pollard JE, Cohen RB. 1988. Ultrasensitive detection of atmospheric constituents by supersonic molecular beam, multiphoton ionization mass spectroscopy. El Segundo, CA Aerospace Corp. NTIS No. AD-A202-299. 

Brady BB, Peteanu L, Levy DH (1988) The electronic spectra of the pyrimidine bases uracil and thymine in a supersonic molecular beam. Chem Phys Lett 147 538... 

The molecular beam is formed by the supersonic expansion of gas through a pulsed nozzle. It is then collimated by two skimmers, and enters... 

Of course, commercially available transition metal complexes are stable at room temperature because they have achieved an 18-electron noble gas-like electronic configuration. Thus, molecules like iron pentacarbonyl [Fe(CO)s], ferrocene [Fe(C5H5)2], as well as piano-stool complexes such as C5H5Co(CO)2 are chemically quite inert. In order to study bimolecular reactions, it is necessary to first prepare unsaturated complexes. For studies using molecular beams, one approach is through photolysis of a stable volatile precursor in a supersonic nozzle. 

Pyrolysis method involves thermal decomposition of suitable precursors to produce free radicals. Pyrolysis sources based on continuous molecular beam nozzles are well developed (for example, methyl6 8 and benzyl9). Recently, Chen and co-workers have pioneered a flash pyrolysis/supersonic jet technique to produce free radical beams (Fig. I).10 In this radical... 

A technique which is not a laser method but which is most useful when combined with laser spectroscopy (LA/LIF) is that of supersonic molecular beams (27). If a molecule can be coaxed into the gas phase, it can be expanded through a supersonic nozzle at fairly high flux into a supersonic beam. The apparatus for this is fairly simple, in molecular beam terms. The result of the supersonic expansion is to cool the molecules rotationally to a few degrees Kelvin and vibrationally to a few tens of degrees, eliminating almost all thermal population of vibrational and rotational states and enormously simplifying the LA/LIF spectra that are observed. It is then possible, even for complex molecules, to make reliable vibronic assignments and infer structural parameters of the unperturbed molecule therefrom. Molecules as complex as metal phthalocyanines have been examined by this technique. 

Emission spectra of radical cations are obtained by vacuum UV ionization and subsequent laser excitation in noble-gas matrices (see below), or by electron-impact ionization of a beam of neutral parent molecules at energies above the first ionic excited state. After internal conversion to the first excited state, emission may compete more or less successfully with radiationless deactivation. If the experiment is carried out on a supersonic molecular beam one obtains highly resolved emission spectra which, in the case of small molecules, may contain sufficient information to allow a determination of the molecular structure. 

L.G. Randall and A.L. Wahrhaftig, Direct coupling of a dense (supercritical) gas chromatograph to a mass spectrometer using a supersonic molecular beam interface, Rev. Sci. Instrum., 52 (1981) 1283-1295. 

Supersonic molecular beams are used to produce velocities of the molecules in the reactant beams. For generating the supersonic molecular beam, the... 

Campargue R (1984) Progress in overexpanded supersonic jets and skimmed molecular beams in free zones of silence. J Phys Chem A 88 4466-4474... 

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