TY - JOUR
T1 - Electron transfer in multiply bridged donor-acceptor molecules
T2 - Dephasing and quantum coherence
AU - Goldsmith, Randall H.
AU - Wasielewski, Michael R.
AU - Ratner, Mark A.
PY - 2006/10/19
Y1 - 2006/10/19
N2 - We present a simple theoretical treatment of nonadiabatic electron transfer in multiply bridged donor-bridge-acceptor molecules using the density matrix formalism. Destructive interference can result from different signed couplings between bridge sites, with the simplest system being a four-site Joachim-type molecular interferometer. Previous work has shown that deposition of energy on the bridge sites erases the interference and recovers transport. We show that pure local dephasing, a completely elastic process, is also capable of eliminating destructive interference and regaining transport. Destructive interference as a result of system connectivity can explain the familiar ortho-meta-para reactivity of benzene bridges. We also show that pure dephasing can yield a coalescence of ortho, meta, and para effective coupling strengths and suggest a system to observe this effect experimentally.
AB - We present a simple theoretical treatment of nonadiabatic electron transfer in multiply bridged donor-bridge-acceptor molecules using the density matrix formalism. Destructive interference can result from different signed couplings between bridge sites, with the simplest system being a four-site Joachim-type molecular interferometer. Previous work has shown that deposition of energy on the bridge sites erases the interference and recovers transport. We show that pure local dephasing, a completely elastic process, is also capable of eliminating destructive interference and regaining transport. Destructive interference as a result of system connectivity can explain the familiar ortho-meta-para reactivity of benzene bridges. We also show that pure dephasing can yield a coalescence of ortho, meta, and para effective coupling strengths and suggest a system to observe this effect experimentally.
UR - http://www.scopus.com/inward/record.url?scp=33751268269&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33751268269&partnerID=8YFLogxK
U2 - 10.1021/jp0639187
DO - 10.1021/jp0639187
M3 - Article
C2 - 17034204
AN - SCOPUS:33751268269
SN - 1520-6106
VL - 110
SP - 20258
EP - 20262
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 41
ER -