We address relaxation pathways in the excited singlet states 5, of saturated molecules, specifically alkylated oligosilanes. Unlike their longer peralkylated homologues, disilanes and trisilanes do not fluoresce even at low temperatures. An examination of the S-1 potential energy surface of Si3Me8 with density functional (TDDFT, LC-TDDFT), and ab initio (RICC2, RIADC(2)) methods with TZVP basis sets revealed only extremely shallow minima in the vicinity of funnels, accounting for the absence of fluorescence, rapid internal conversion, and photoproducts. Relaxed singlet excited state structures either contain one approximately trigonal bipyramidal Si atom or two that are halfway between tetrahedral and trigonal bipyramidal. Four of the ligands are those that the Si atom had in the ground state. Natural bond orbital analysis suggests that the fifth one is a nonbonding hybrid orbital of the lone-pair type and size intermediate between valence and Rydberg, with an only very small occupancy, yet stereochemically active. The fifth natural hybrid orbital is composed primarily of 4s, 4p, and usually to a lesser degree, also 3d atomic orbitals. The trigonal bipyramidal structure allows an optimal accommodation of the presence of both a negative and a positive charge in the Lewis structures. The excess negative charge on the distorted Si atom is shared between the nonbonding fifth hybrid orbital and sigma* antibonding orbitals associated with its bonds. The positive charge resides in an adjacent sigma SiSi bond orbital. A Rydberg minimum also occurs on the S, surface at the geometry of the radical cation.