Single-electron wavefunctions, or orbitals, are the mathematical constructs used to describe the multi-electron wavefunction of molecules. Because the highest-lying orbitals are responsible for chemical properties, they are of particular interest. To observe these orbitals change as bonds are formed and broken is to observe the essence of chemistry. Yet single orbitals are difficult to observe experimentally, and until now, this has been impossible on the timescale of chemical reactions. Here we demonstrate that the full three-dimensional structure of a single orbital can be imaged by a seemingly unlikely technique, using high harmonics generated from intense femtosecond laser pulses focused on aligned molecules. Applying this approach to a series of molecular alignments, we accomplish a tomographic reconstruction of the highest occupied molecular orbital of N2. The method also allows us to follow the attosecond dynamics of an electron wave packet.
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In addition to the NRC, we acknowledge financial support from the National Science and Engineering Research Council, Photonic Research Ontario, the Canadian Institute for Photonic Innovation, the Alexander von Humboldt-Stiftung and the Japan Society for the Promotion of Science. We thank M. Yu. Ivanov, M. Spanner, J. P. Marangos, M. Lein, P. H. Bucksbaum, I. A. Walmsley, D. Jonas, J. Tse and J. G. Underwood for discussions.
The authors declare that they have no competing financial interests.
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Itatani, J., Levesque, J., Zeidler, D. et al. Tomographic imaging of molecular orbitals. Nature 432, 867–871 (2004). https://doi.org/10.1038/nature03183
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