Anisotropy of the electric field gradient in two-dimensional alpha-MoO_(3) investigated by (57)^Mn((57)^Fe) emission mossbauer spectroscopy

Abstract

Van der Waals alpha-MoO_(3) samples offer awide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mossbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing alpha-MoO_(3) samples. Although alpha-MoO3 is a twodimensional (2D) material, scanning electron microscopy shows that the crystals are 0.5-5-mu m thick. The combination of X-ray diffraction and micro-Raman spectroscopy, performed after sample preparation, provided evidence of the phase purity and crystal quality of the samples. The eMS measurements were conducted following the implantation of (57)^Mn (t(1/ 2) = 1.5 min), which decays to the (57)^Fe, 14.4 keV Mossbauer state. The eMS spectra of the samples are dominated by a paramagnetic doublet (D1) with an angular dependence, pointing to the Fe^(2+) probe ions being in a crystalline environment. It is attributed to an asymmetric EFG at the eMS probe site originating from strong in-plane covalent bonds and weak out-of-plane van derWaals interactions in the 2D material. Moreover, a second broad component, D2, can be assigned to Fe^(3+) defects that are dynamically generated during the online measurements. The results are compared to ab initio simulations and are discussed in terms of the in-plane and out-of-plane interactions in the system