| Abstract: | INDO parameterized calculations, employing phosphorus s, p and d valence orbitals, are reported for values of 1J(PC) and 1J(PF) relating to phosphorus in formal tri- and pentavalent states. The 1J(PC), interactions are mainly controlled by the contact term. Thus, trivalent phosphorus compounds have negative values for 1J(PC), whereas those for pentavalent phosphorus are positive due to the s lone-pair effect. The inclusion of phosphorus 3d orbitals is shown to be important for an understanding of the processes contributing to 1J(PF) interactions. 1J(PF) values are shown to be negative for both tri- and pentavalent phosphorus compounds. The contact and orbital interactions are significant for the trivalent phosphorus molecules, whereas in the pentavalent phosphorus case 1J(PF) is dominated by the orbital term. |
