Production of high density molecular beams with wide velocity scanning.

We describe modifications of a pulsed rotating supersonic beam source that improve performance, particularly increasing the beam density and sharpening the pulse profiles. As well as providing the familiar virtues of a supersonic molecular beam (high intensity, narrowed velocity distribution, and drastic cooling of rotation and vibration), the rotating source enables scanning the translational velocity over a wide range. Thereby, beams of any atom or molecule available as a gas can be slowed or speeded. Using Xe beams in the slowing mode, we have obtained lab speeds down to about 40 ± 5 m/s with density near 10(11) cm(-3) and in the speeding mode lab speeds up to about 660 m/s and density near 10(14) cm(-3). We discuss some congenial applications. Providing low lab speeds can markedly enhance experiments using electric or magnetic fields to deflect, steer, or further slow polar or paramagnetic molecules. The capability to scan molecular speeds facilitates merging velocities with a codirectional partner beam, enabling study of collisions at very low relative kinetic energies, without requiring either beam to be slow.

Pulsed rotating supersonic source for merged molecular beams.

We describe a pulsed rotating supersonic beam source, evolved from an ancestral device [M. Gupta and D. Herschbach, J. Phys. Chem. A 105, 1626 (2001)]. The beam emerges from a nozzle near the tip of a hollow rotor which can be spun at high-speed to shift the molecular velocity distribution downward or upward over a wide range. Here we consider mostly the slowing mode. Introducing a pulsed gas inlet system, cryocooling, and a shutter gate eliminated the main handicap of the original device in which continuous gas flow imposed high background pressure. The new version provides intense pulses, of duration 0.1-0.6 ms (depending on rotor speed) and containing ∼10(12) molecules at lab speeds as low as 35 m/s and ∼10(15) molecules at 400 m∕s. Beams of any molecule available as a gas can be slowed (or speeded); e.g., we have produced slow and fast beams of rare gases, O(2), Cl(2), NO(2), NH(3), and SF(6). For collision experiments, the ability to scan the beam speed by merely adjusting the rotor is especially advantageous when using two merged beams. By closely matching the beam speeds, very low relative collision energies can be attained without making either beam very slow.

Tuning DNA "strings": modulating the rate of DNA replication with mechanical tension.

Recent experiments have measured the rate of replication of DNA catalyzed by a single enzyme moving along a stretched template strand. The dependence on tension was interpreted as evidence that T7 and related DNA polymerases convert two (n = 2) or more single-stranded template bases to double helix geometry in the polymerization site during each catalytic cycle. However, we find structural data on the T7 enzyme--template complex indicate n = 1. We also present a model for the "tuning" of replication rate by mechanical tension. This model considers only local interactions in the neighborhood of the enzyme, unlike previous models that use stretching curves for the entire polymer chain. Our results, with n = 1, reconcile force-dependent replication rate studies with structural data on DNA polymerase complexes.

Fifty years in physical chemistry: homage to mentors, methods, and molecules.

A nostalgic account is given of my scientific odyssey, recalling early encounters, some fateful, some just fun, with mentors, methods, and molecules. These include stories of my student years at Stanford, pursuing chemical kinetics with Harold Johnston; graduate study at Harvard, doing molecular spectroscopy with Bright Wilson; and fledgling faculty years at Berkeley, launching molecular beam studies of reaction dynamics. A few vignettes from my "ever after " era on the Harvard faculty emphasize thematic motivations or methods inviting further exploration. An Appendix provides a concise listing of colleagues in research and the topics we have pursued.

Generation of "bastard" molecular ions from van der Waals clusters: Ar(n)(C(2)Cl(4))(m) ions, suspected interlopers in collection of solar neutrinos.

Gaseous molecular ions containing argon and perchlorethylene, Ar(n)(C(2)Cl(4))(m) (+) in which n >/= 1-29 and m >/= 1-4, are produced by electron bombardment of van der Waals clusters formed by expanding an Ar/C(2)Cl(4) mixture through a supersonic nozzle. Previous attempts to observe such ions in a high-pressure mass spectrometer were not successful, as with many other ("bastard") ions that similarly lack a stable chemically bound neutral parent molecule. This is probably due to dissociation induced by the large exoergicity from charge transfer between species that differ greatly in ionization potential. Use of van der Waals clusters as parent species avoids entirely the exoergicity problem and thus offers a general method to generate bastard ions. The Ar(C(2)Cl(4))(m) (+) ions have been suspected of interfering with collection of (37)Ar(+) ions produced by the (37)Cl(v,e(-))(37)Ar(+) reaction in the solar neutrino observatory. Although, as shown by our results, these ions are stable, they are unlikely to inhibit collection on the long time scale of the solar neutrino experiment.