Nonvalence Correlation-Bound Anionic States: A New Doorway to Electron Transfer
The mechanistic details and the dynamics of electron transfer to molecules continue to be poorly understood. The key to unraveling this fundamentally important chemical process hinges upon a sound understanding of electron binding states. Here I will discuss the discovery, theoretical characterization and role of nonvalence correlation-bound (NVCB) states as a new low-energy doorway for electron capture and transfer. In the NVCB states of anions, the excess electron occupies a very diffuse orbital while its binding to the molecule or cluster is dominated by long-range dispersion-type correlation forces. Ab initio methods and one-electron model Hamiltonians will be used to characterize the NVCB anionic states. The existence of NVCB states and its implications for gas- and condensed-phase electron transfer will be illustrated using examples ranging from small molecules to large fullerene systems.
- V. K. Voora, A. Kairalapova, T. Sommerfeld, and K. D. Jordan. “Theoretical approaches for treating non-valence correlation-bound anions”, J. Chem. Phys., 2017, 147, 214114.
- V. K. Voora, and K. D. Jordan. “Nonvalence correlation-bound anion states of spherical fullerenes”, Nano Lett., 2014, 14, 4602.
- V. K. Voora, L. S. Cederbaum, and K. D. Jordan. “Existence of a correlation bound s-type anion state of C60”, J. Phys. Chem. Lett., 2013, 4, 849.
- J. P. Rogers, C. S. Anstöter, and J. R. R. Verlet. “Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state”, Nat. Chem., 2018, http://dx.doi.org/10.1038/nchem.2912.