Probing the in‐plane dipole moment vector between ground and excited state of single molecules by the Stark effect

With four electrodes we tune the angle of the in-plane electric field and we measure the shift of the single molecule's narrow resonance. These shifts as a function of the electric field angle allow us to resolve the direction and magnitude of the permanent dipole moment between ground and excited state.

Abstract

Single molecules, embedded inside a well-defined insertion site of a single-crystalline host matrix, are sensitive probes of electric field via the induced Stark shift on their lifetime-limited electronic transition. Though the response of molecules to electric field has been shown to be relatively homogeneous, crystal symmetry allows for several, spectroscopically-indistinguishable, orientations of the net permanent dipole moment between the ground and excited state – the dipole vector – and this is problematic for measuring field orientation and magnitude. In this work, we measure for each terrylene molecule, embedded inside a new host matrix, the dipole vector independently by an electric field that we can rotate in the plane of the crystal. This single crystal host matrix, called [1]BenzoThieno[3,2-b]BenzoThiophene, induces a moderate symmetry breaking of the embedded centrosymmetric terrylene molecule, and gives rise to a net dipole moment of 0.28±0.09 Debye. Based on quantum chemistry calculations we propose an insertion site that best matches the experimental findings.

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