Asymmetry sum rule for molecular predissociation

© 2000 American Physical SocietyIn the case of weak diatomic molecular predissociation by noninteracting, optically inactive continuum states, it is demonstrated that the predissociation line shape is more accurately represented by a Beutler-Fano profile than by a Lorentzian. The weak asymmetry that is found to occur is due principally to interactions with neighboring vibrational resonances. For this type of predissociation in the case of multiple continua, a sum rule for the corresponding line-shape asymmetry is derived. This sum rule is verified numerically using single-channel and multichannel coupled Schrödinger-equation calculations for the Schumann-Runge band system of O2. Similar results are presented for the case of optically active continua.F. T. Hawes, L. W. Torop, B. R. Lewis and S. T. Gibso

Trends and transitions in the institutional environment for public and private science

The last quarter-century bore witness to a sea change in academic involvement with commerce. Widespread university-based efforts to identify, manage, and market intellectual property (IP) have accompanied broad shifts in the relationship between academic and proprietary approaches to the dissemination and use of science and engineering research. Such transformations are indicators of institutional changes at work in the environment faced by universities. This paper draws upon a fifteen-year panel (1981–1995) of university-level data for 87 research-intensive US campuses in order to document trends and transitions in relationships among multiple indicators of academic and commercial engagement. The institutional environment for public and private science is volatile, shifting in fits and starts from a situation conducive to organizational learning through high volume patenting to a more challenging arrangement that links indiscriminate pursuit of IP with declines in both the volume and impact of academic science. The pattern and timing of these transitions may support an enduring system of stratification that offers increasing returns to first-movers while limiting the opportunities available to universities that are later entrants to the commercial realm. Unpacking the systematic effects of university research commercialization requires focused attention on the sources and trajectories of profound institutional change.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/42839/1/10734_2004_Article_2916.pd

Solution Dynamics of Redox Noninnocent Nitrosoarene Ligands: Mapping the Electronic Criteria for the Formation of Persistent Metal-Coordinated Nitroxide Radicals

The redox-noninnocence of metal-coordinated C-organo nitrosoarenes has been established on the basis of solid-state characterization techniques, but the solution-phase properties of this class of metal-coordinated radicals have been relatively underexplored. In this report, the solution-phase properties and dynamics of the bis-nitrosobenzene diradical complex trans-Pd(κ1-N-PhNO)2(CNArDipp2)2 are presented. This complex, which is best described as containing singly reduced phenylnitroxide radical ligands, is shown to undergo facile nitrosobenzene dissociation in solution to form the metalloxaziridine Pd(η2-N,O-PhNO)(CNArDipp2)2 and thus is not a persistent species in solution. An equilibrium between trans-Pd(κ1-N-PhNO)2(CNArDipp2)2, Pd(η2-N,O-PhNO)(CNArDipp2)2, and free nitrosobenzene is established in solution, with the metalloxaziridine being predominantly favored. Efforts to perturb this equilibrium by the addition of excess nitrosobenzene reveal that the formation of trans-Pd(κ1-N-PhNO)2(CNArDipp2)2 is in competition with insertion-type chemistry of Pd(η2-N,O-PhNO)(CNArDipp2)2 and is therefore not a viable strategy for the production of a kinetically persistent bis-nitroxide radical complex. Electronic modification of the nitrosoarene framework was explored as a means to generate a persistent trans-Pd(κ1-N-ArNO)2(CNArDipp2)2 complex. While most substitution schemes failed to significantly perturb the kinetic lability of the nitrosoarene ligands in the corresponding trans-Pd(κ1-N-ArNO)2(CNArDipp2)2 complexes, utilization of para-formyl or para-cyano nitrosobenzene produced bis-nitroxide diradical complexes that display kinetic persistence in solution. The origin of this persistence is rationalized by the ability of para-formyl- and para-cyano-aryl groups to both attenuate the trans effect of the corresponding nitrosoarene and, more importantly, delocalize spin density away from the aryl-nitroxide NO unit. The results presented here highlight the inherent instability of metal-coordinated nitroxide radicals and suggest a general synthetic strategy for kinetically stabilizing these species in solution