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On the effect of nuclear bridge modes on donor–acceptor electronic coupling in donor–bridge–acceptor molecules
- Source :
-
Chemical Physics . Mar2009, Vol. 358 Issue 1/2, p45-51. 7p. - Publication Year :
- 2009
-
Abstract
- Abstract: We report a theoretical study of intra-molecular electronic coupling in a symmetric DBA (donor–bridge–acceptor) complex, in which a donor electronic site is coupled to an acceptor site by way of intervening orbitals of a molecular bridge unit. In the off-resonant (deep tunneling) regime of electronic transport, the lowest unoccupied molecular orbitals (MO’s) of the DBA system are split into distinguishable donor/acceptor and bridge orbitals. The effect of geometrical changes at the bridge on the donor/acceptor electronic energy manifold is studied for local stretching and bending modes. It is demonstrated that the energy splitting in the manifold of donor/acceptor unoccupied MOs changes in response to such changes, as assumed in simple McConnell-type models. Limitations of the simple models are revealed where the electronic charging of the bridge orbitals correlates with increasing donor/acceptor orbital energy splitting only for stretching but not for bending bridge modes. [Copyright &y& Elsevier]
Details
- Language :
- English
- ISSN :
- 03010104
- Volume :
- 358
- Issue :
- 1/2
- Database :
- Academic Search Index
- Journal :
- Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 37161607
- Full Text :
- https://doi.org/10.1016/j.chemphys.2008.12.016