where EELEC represent the permanent Coulombic electrostatic interactions between fragmental charge distributions. EPOL is polarization energy term, resulting from the intramolecular density relaxation due to the perturbating presence of the other fragment in the complex. ECT is the charge transfer energy term, accounting for the stabilization due to the inter-and intra-molecular charge flow in the fragments after the complex formation ; note that ECT is not the number of electrons transferred between fragments. EDISP stands for stabilizing dispersion forces. EPREP is the preparation energy, tracking the energy penalty due to the geometric/electronic preparation of the fragments to reach the complex geometry. Finally, EPAULI stands for the steric repulsion of electrons with the same spin when two fragments are compressed (Pauli principle). previously reported (Table ). Polyhedral/structural representations of the TMPhos systems are displayed in Fig. . A polyhedral representation is useful to get a clear view of the coordination sphere of a metalcentered array, which is related to the exerted crystal field by atoms surrounding the dopants. Figs. show that in the substitutionally doped phosphorene nanosheets (TMSPhos), the metal atom form up to four TM-P bonds (d1, d2, d3, and d4 in Fig. ) with bond distances ranging from 2.2 to 2.9 Å (Fig. ). Moreover, a fifth metal-P bond (dh) is perpendicular to the plane of the d1-4 bonds in a downwards direction not longer than 2.6 Å; the bonding can be associated to a metal-centered square pyramid geometry based on a TM-P5 coordination unit as noted from the polyhedral representation (Fig ). The exceptions are the CuSPhos and ZnSPhos systems, where dopants form up to two bonds with bond length values of 2.2-2.3 Å. It is also noticed that d3 and d4 TM-P bond distances are longer than 2.9 Å (Fig. ), resembling the bond distance that the P atom has on pristine phosphorene. In the case of the adatom doped phosphorene (TMAPhos), the adatom prefers to stay at the hollow site of one hexagonal ring and bonded with three P atoms .