Theoretical and Computational Chemistry

First Principle Investigations of Long-range Magnetic Exchange Interactions via Polyacene Coupler

Prabhleen Kaur Institute of Nano Science and Technology
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Abstract

The electronic and magnetic properties of polyacenes become quite fascinating as the number of linearly conjugated benzene rings increases. Higher-order conjugated polyacenes develop radicaloid characters due to the transition of electronic structures from closed-shell to the open-shell system. Here we have investigated the role of such polyacenes as the magnetic coupler when placed between the two spin-sources based on nitroxy radicals. To do so, the magnetic exchange interactions (2J) are computed employing electronic structure theories, i.e. broken-symmetry (BS) approach within the density functional theory (DFT) as well as symmetry-adopted wave function based multi-configurational methods. In the former approach, various genre of exchange-correlation (XC) functionals such as generalized gradient approximation (GGA), meta-GGA, hybrid functional, constrained spin density (i.e. CDFT) and on-site Coulomb correlation corrected GGA+U functionals are adopted. All DFT based calculations estimate an exponential increase in 2J values with the length of the couplers, especially for the higher-order acenes. This is indeed an unexpected observation and also there is no experimental report available in support of the DFT calculations. The complexity in the electronic structure enhances with the increasing number of benzene rings due to an increase in near-degenerate or quasi-degenerate molecular orbitals (MOs) and also the reduction of the energy gap with the low-lying excited states. Consequently, it invokes a severe challenge in the computations of the magnetic exchange interactions in DFT. As an alternative approach, the wave function based multi-reference calculations, e.g. CASSCF/NEVPT2 methods are also adopted. In the later calculations, it has been realized that the π-orbitals of the couplers play a crucial role in the exchange interactions. For larger polyacenes (i.e. hexacene to decacene) such calculations become prohibitively expensive and rigorous as the number of π-orbitals increases, thus expanding the active space enormously. The limited active spaces calculations indicate quite strong ferromagnetic exchange interactions, thus in principle, reinforcing long-range magnetic exchange interactions.

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Supplementary material

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Long-range-magnetic-exchange SI