Probing the Roles of Temperature and Cooperative Effects in Chirality-Induced Spin Selectivity: Photoelectron Spin Polarization in Helical Tetrapyrroles.

We investigate the roles of molecular vibrations and intermolecular interactions in the mechanism underlying chirality-induced spin selectivity (CISS) in monolayers of helical tetrapyrrole (TPBT) molecules. The spin polarization of photoelectrons emitted from TPBT-functionalized Cu(111) surfaces was measured as a function of the temperature and the surface coverage. We employed DFT calculations to determine the energy and temperature-dependent population of vibrational modes which vary either the molecular pitch and/or the molecular radius. In combination, the data demonstrate that molecular vibrations do not play a significant role for CISS in the TPBT layers. Submonolayer coverages were created by gradual thermal desorption of the molecules from the surface during the spin polarization measurements. While the spin polarization scales nonlinearly with the surface coverage, this behavior can be rationalized entirely through changes of the photoelectron yield upon surface functionalization, and therefore represents no evidence for cooperative effects involved in CISS.