Structural Diversity and Electronic Properties of 3d Transition Metal Tetraphosphides, TMP₄ (TM = V, Cr, Mn, and Fe)

Abstract

Transition-metal (TM) phosphides attract increasing attention with applications for energy conversion and storage, due to their outstanding physical, chemical, and electronic properties. The 3d transition metal tetraphosphides (TMP, TM = V, Cr, Mn, and Fe) possess multiple allotropies and rich electronic properties. Here, we perform the investigations of the structural, electronic, and elastic properties for 3d-TMP (TM = V, Cr, Mn, and Fe) using density functional theory (DFT) calculations. These compounds are featured with alternating buckled phosphorus sheets with ten-numbered phosphorus rings and varied transition-metal layers. Hybrid DFT calculations reveal that TMP compounds exhibit a wide range of electrical properties, ranging from metallic behavior for VP to semiconducting behavior for CrP with the narrow direct band gap of 0.63 eV to enlarged semiconducting MnP and FeP with band gap of 1.6-2.1 eV. The bonding analysis indicates that P-P and TM-P covalent interactions dominate in the phosphorus sheets and TMP octahedrons, which are responsible for the structural and electronic diversity.

Novel electronic properties of monoclinic MP4 (M = Cr, Mo, W) compounds with or without topological nodal line

“…The calculated equilibrium lattice parameters, bond lengths, and bond angles for compounds are listed in Table 2 . It is seen that our calculated structural parameters matches well with the reported experimental and calculated data 55 , 58 , 59 .…”

“…It is seen that our calculated structural parameters matches well with the reported experimental and calculated data 55 , 58 , 59 .…”

“…For as shown in Fig. 3 a, the conduction band minimum (CBM) is located along H-Z direction and valence band maximum (VBM) is located along F-H direction, showing a semiconducting behavior with an indirect band gap of 0.47 eV, which is smaller than the reported direct band gap of 0.63 eV 58 . For as shown in Fig.…”

“…S2 in Supplementary Information, respectively. The structural parameters and electronic behavior that is, is metallic and is a semiconductor reported by Gong et al 58 . We find that ( , Nb, Ta) have metallic behavior, while VIIB- ( , Tc, Re) are semiconductors.…”

Manganese Tetraphosphide (MnP4) as a High Capacity Anode for Lithium‐Ion and Sodium‐Ion Batteries

“…This variation of electronic structure was also observed in other TMP 4 (TM = V, Cr, and Fe) phases, which have the similar crystal structure to MnP 4 . [ 32 ] The electronic structure calculation for TMP 4 (TM = V, Cr, and Fe) indicated that VP 4 showed a continuous band energy indicating the metallic behavior and CrP 4 showed a relatively narrow bandgap of 0.63 eV than that of MnP 4 . On the other hand, three different FeP 4 polymorphs showed the relatively large band gaps of 1.76, 1.83, and 2.13 eV, respectively, with the semiconducting behavior.…”