Laser-induced nuclear magnetic resonance splitting in hydrocarbons

Abstract

Irradiation of matter with circularly polarized light (CPL) shifts all nuclear magnetic resonance (NMR) lines. The phenomenon arises from the second-order interaction of the electron cloud with the optical field, combined with the orbital hyperfine interaction. The shift occurs in opposite directions for right and left CPL, and rapid switching between them will split the resonance lines into two. We present ab initio and density functional theory predictions of laser-induced NMR splittings for hydrocarbon systems with different sizes: ethene, benzene, coronene, fullerene, and circumcoronene. Due to the computationally challenging nature of the effect, traditional basis sets could not be used for the larger systems. A novel method for generating basis sets, mathematical completeness optimization, was employed. As expected, the magnitude of the spectral splitting increases with the laser beam frequency and polarizability of the system. Massive amplification of the effect is also observed close to the optical excitation energies. A much larger laser-induced splitting is found for the largest of the present molecules than for the previously investigated noble gas atoms or small molecules. The laser intensity required for experimental detection of the effect is discussed.