A Multiconfigurational Wave Function Theoretical Study on Electronic Structure and Magnetic Susceptibility of Dilanthanide Single Molecule Magnet

Single molecule magnets (SMMs) have been a promising material for next-generation high-density information storage and molecular spintronics. N-2(3-)-bridged dilanthanide complexes, {[(Me3Si)(2)N](2)Ln(THF)(mu-eta(2):eta(2)-N-2)(THF)Ln[(Me3Si)(2)N](2)}(1-), exhibit high blocking temperatures and have been one of the promising candidates for future application. Rational understanding should be established between the magnetic properties and electronic structure. However, the theoretical study is still challenging due to the complexities in their electronic structures. Here, we theoretically studied the magnetic susceptibility of dilanthanide SMMs based on the state-of-the-art multistate-complete active space self-consistent field and perturbation theory at the second order and restricted active space state interaction with spin-orbit coupling calculations. Temperature dependence of the magnetic susceptibility (chi T-m-T curve) was quantitatively reproduced by the theoretical calculations. The complexities in the electronic states of these dilanthanide complexes originate from significantly strong static electron correlations in the lanthanide 4f and N-2 pi* orbitals and the SOC effect. The temperature dependence of the magnetic susceptibility results from the energy levels and magnetic properties of the low-lying excited state. The chi T-m values below 50 K are dominated by the ground state, while thermal distribution in the low-lying excited state affects the chi T-m values over 50 K. Saturation magnetization at low temperatures was also evaluated, and the result agrees with the experimental observation.