Ultrafast large-amplitude relocation of electronic charge in ionic crystals.

Zamponi, Flavio; Rothhardt, Philip; Stingl, Johannes; Woerner, Michael; Elsaesser, Thomas · Proc Natl Acad Sci U S A · 2012

basic_science · Level V

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Abstract

The interplay of vibrational motion and electronic charge relocation in an ionic hydrogen-bonded crystal is mapped by X-ray powder diffraction with a 100 fs time resolution. Photoexcitation of the prototype material KH(2)PO(4) induces coherent low-frequency motions of the PO(4) tetrahedra in the electronically excited state of the crystal while the average atomic positions remain unchanged. Time-dependent maps of electron density derived from the diffraction data demonstrate an oscillatory relocation of electronic charge with a spatial amplitude two orders of magnitude larger than the underlying vibrational lattice motions. Coherent longitudinal optical and tranverse optical phonon motions that dephase on a time scale of several picoseconds, drive the charge relocation, similar to a soft (transverse optical) mode driven phase transition between the ferro- and paraelectric phase of KH(2)PO(4).