Correlating the motion of electrons and nuclei with two-dimensional electronic–vibrational spectroscopy

• DOI: 10.1073/pnas.1409207111
• Publication Date: 2014-06-10T07:46:19Z
• Authors: Thomas A. A. Oliver; Nicholas H. C. Lewis; Graham R. Fleming
• Keywords: 540; 530; 7. Clean energy

Significance To have a full understanding of the role of nuclear motions involved in nonradiative relaxation dynamics of complex molecular systems such as carotenoids, nanomaterials, and molecular photoswitches, the ability to correlate the electronic and nuclear degrees of freedom is imperative. We have developed 2D electronic–vibrational spectroscopy to observe this correlation, and this new spectroscopic technique will provide a direct probe of the coupling between electronic and nuclear dynamics at conical intersections, and thus the underlying mechanisms driving the ensuing photochemistry.