Origin of Axial and Radial Expansions in Carbon Nanotubes Revealed by Ultrafast Diffraction and Spectroscopy
The coupling between electronic and nuclear degrees of freedom in low-dimensional, nanoscale systems plays a fundamental role in shaping many of their properties. Here, we report the disentanglement of axial and radial expansions of carbon nanotubes, and the direct role of electronic and vibrational excitations in determining such expansions. With subpicosecond and subpicometer resolutions, structural dynamics were explored by monitoring changes of the electron diffraction following an ultrafast optical excitation, whereas the transient behavior of the charge distribution was probed by time-resolved, electron-energy-loss spectroscopy. Our experimental results, and supporting density functional theory calculations, indicate that a population of the excited carriers in the antibonding orbitals of the nanotube walls drives a transient axial deformation in ∼1 ps; this deformation relaxes on a much longer time scale, 17 ps, by nonradiative decay. The electron-driven expansion is distinct from the phonon-driven dynamics observed along the radial direction, using the characteristic Bragg reflections; it occurs in 5 ps. These findings reveal the nonequilibrium distortion of the unit cell at early times and the role of the electron(phonon)-induced stress in the lattice dynamics of one-dimensional nanostructures.
Additional Information© 2015 American Chemical Society. Received for review November 16, 2014 and accepted January 28, 2015. Publication Date (Web): January 30, 2015. This work was supported by the National Science Foundation and the Air Force Office of Scientific Research in the Center for Physical Biology at Caltech funded by the Gordon and Betty Moore Foundation. G.M.V. gratefully acknowledge Dr. W. Liang for assistance during UEC experiments. We thank Dr. S. Schäfer, Dr. S. T. Park, Dr. J. Hu for helpful discussions, and Dr. N. Manini for his suggestions and confirmations of the results of the ab initio calculations that were performed in this paper.
Supplemental Material - nn506524c_si_001.pdf