TY - JOUR
T1 - Through-bond and through-space coupling in photoinduced electron and energy transfer
T2 - An ab initio and semiempirical study
AU - Clayton, Andrew H.A.
AU - Scholes, Gregory D.
AU - Ghiggino, Kenneth P.
AU - Paddon-Row, Michael N.
PY - 1996/6/27
Y1 - 1996/6/27
N2 - Ab initio and semiempirical calculations of transfer integrals for electron transfer and energy transfer have been carried out on rigidly linked norbornane-bridged naphthalene dimers to gain insight into the relative importance of through-bond and through-space interactions on photoinduced energy and electron transfer processes. In the absence of direct through-space orbital overlap between the naphthalene moieties, through-bond interaction involving the linking polynorbornane bridge is found to significantly enhance the transfer integrals for electron transfer and triplet-triplet energy transfer. For singlet-singlet energy transfer direct through-space Coulombic interaction between the naphthalene moieties is non-negligible at the separations considered and acts to reinforce the through-bond interaction. The relationship between electron and energy transfer processes and the application of these results to the interpretation of recent experimental data are discussed.
AB - Ab initio and semiempirical calculations of transfer integrals for electron transfer and energy transfer have been carried out on rigidly linked norbornane-bridged naphthalene dimers to gain insight into the relative importance of through-bond and through-space interactions on photoinduced energy and electron transfer processes. In the absence of direct through-space orbital overlap between the naphthalene moieties, through-bond interaction involving the linking polynorbornane bridge is found to significantly enhance the transfer integrals for electron transfer and triplet-triplet energy transfer. For singlet-singlet energy transfer direct through-space Coulombic interaction between the naphthalene moieties is non-negligible at the separations considered and acts to reinforce the through-bond interaction. The relationship between electron and energy transfer processes and the application of these results to the interpretation of recent experimental data are discussed.
UR - http://www.scopus.com/inward/record.url?scp=0000907960&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000907960&partnerID=8YFLogxK
U2 - 10.1021/jp953532o
DO - 10.1021/jp953532o
M3 - Article
AN - SCOPUS:0000907960
SN - 0022-3654
VL - 100
SP - 10912
EP - 10918
JO - Journal of physical chemistry
JF - Journal of physical chemistry
IS - 26
ER -