The Hydrated Excess Proton in the Zundel Cation H5O2+: The Role of Ultrafast Solvent Fluctuations

The nature of the excess proton in liquid water has remained elusive after decades of extensive research. In view of ultrafast structural fluctuations of bulk water scrambling the structural motifs of excess protons in water, we selectively probe prototypical protonated water solvates in acetonitrile on the femtosecond time scale. Focusing on the Zundel cation H₅O₂⁺ prepared in room‐temperature acetonitrile, we unravel the distinct character of its vibrational absorption continuum and separate it from OH stretching and bending excitations in transient pump‐probe spectra. The infrared absorption continuum originates from a strong ultrafast frequency modulation of the H⁺ transfer vibration and its combination and overtones. Vibrational lifetimes of H₅O₂⁺ are found to be in the sub‐100 fs range, much shorter than those of unprotonated water. Theoretical results support a picture of proton hydration where fluctuating electrical interactions with the solvent and stochastic thermal excitations of low‐frequency modes continuously modify the proton binding site while affecting its motions.     

Designing Least-Cost Nonblocking Broadband Networks

Integrated network technologies, such as ATM, support multimedia applications with vastly different bandwidth needs, connection request rates, and holding patterns. Due to their high level of flexibility and communication rates approaching several gigabits per second, the classical network planning techniques, which rely heavily on statistical analysis, are less relevant to this new generation of networks. In this paper, we propose a new model for broadband networks and investigate the question of their optimal topology from a worst-case performance point of view. Our model is more flexible and realistic than others in the literature, and our worst-case bounds are among the first in this area. Our results include a proof of intractability for some simple versions of the network design problem and efficient approximation algorithms for designing nonblocking networks of provably small cost. More specifically, assuming some mild global traffic constraints, we show that a minimum-cost nonblockingstarnetwork achieves near-optimal cost; the cost ratio is at most 2 if switch source and sink capacities are symmetric and at most 3 when the total source and sink capacities are balanced. In the special case of unit link costs, we can show that a star network is indeed the cheapest nonblocking network.