Distance dependence of photoinduced long-range electron transfer in zinc/ruthenium-modified myoglobins

Long-range electron transfer.

Recent investigations have shed much light on the nuclear and electronic factors that control the rates of long-range electron tunneling through molecules in aqueous and organic glasses as well as through bonds in donor-bridge-acceptor complexes. Couplings through covalent and hydrogen bonds are much stronger than those across van der Waals gaps, and these differences in coupling between bonded...

Coherent control of long-range photoinduced electron transfer by stimulated X-ray Raman processes.

We show that X-ray pulses resonant with selected core transitions can manipulate electron transfer (ET) in molecules with ultrafast and atomic selectivity. We present possible protocols for coherently controlling ET dynamics in donor-bridge-acceptor (DBA) systems by stimulated X-ray resonant Raman processes involving various transitions between the D, B, and A sites. Simulations presented for a...

Distance dependence of through-bond electron transfer rates in electron-capture and electron-transfer dissociation

Ab initio electronic structure calculations on model cations containing a disulfide linkage and a protonated amine site are carried out to examine ow the rate of electron transfer from a Rydberg orbital on the amine site to the S S * orbital depends upon the distance between these two rbitals. These simulations are relevant to both electron-capture and electron-transfer dissociation mass spectr...

Nonequilibrium photoinduced electron transfer

Driving-Force Effects on the Rate of Long-Range Electron Transfer in Ruthenium-Modified Cytochrome c

Two new Ru-modified, Zn-substituted derivatives of horse heart cytochrome c have been prepared, Rua,L(histi* dine-33)-Zn-cyt c (a = NH3; L = pyridine, isonicotinamide). Molecular mechanics modeling indicates that the 11.7 A edge-to-edge separation between the redox centers is virtually identical with that reported for the Ru-pentaammine derivative. Rates of photoinduced charge separation and re...