title: Toward control of electron transfer in donor-acceptor molecules by bond-specific infrared excitation.
abstract: Electron transfer (ET) from donor to acceptor is often mediated by nuclear-electronic (vibronic) interactions in molecular bridges. Using an ultrafast electronic-vibrational-vibrational pulse-sequence, we demonstrate how the outcome of light-induced ET can be radically altered by mode-specific infrared (IR) excitation of vibrations that are coupled to the ET pathway. Picosecond narrow-band IR excitation of high-frequency bridge vibrations in an electronically excited covalent trans-acetylide platinum(II) donor-bridge-acceptor system in solution alters both the dynamics and the yields of competing ET pathways, completely switching a charge separation pathway off. These results offer a step toward quantum control of chemical reactivity by IR excitation.
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
authors.forename: Milan
authors.initials: M
authors.lastname: Delor
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Scattergood
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK. Central Laser Facility, Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Science and Technology Facilities Council, Chilton, Oxfordshire OX11 0QX, UK.
authors.forename: Igor V
authors.initials: IV
authors.lastname: Sazanovich
authors.affiliation: Central Laser Facility, Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Science and Technology Facilities Council, Chilton, Oxfordshire OX11 0QX, UK.
authors.forename: Anthony W
authors.initials: AW
authors.lastname: Parker
authors.affiliation: Central Laser Facility, Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Science and Technology Facilities Council, Chilton, Oxfordshire OX11 0QX, UK.
authors.forename: Gregory M
authors.initials: GM
authors.lastname: Greetham
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK.
authors.forename: Anthony J H M
authors.initials: AJ
authors.lastname: Meijer
authors.affiliation: Central Laser Facility, Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Science and Technology Facilities Council, Chilton, Oxfordshire OX11 0QX, UK. mike.towrie@stfc.ac.uk julia.weinstein@sheffield.ac.uk.
authors.forename: Michael
authors.initials: M
authors.lastname: Towrie
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK. mike.towrie@stfc.ac.uk julia.weinstein@sheffield.ac.uk.
authors.forename: Julia A
authors.initials: JA
authors.lastname: Weinstein