Using laser induced fluorescence (LIF) and resonance enhanced two-photon ionization (R2PI) spectroscopy, several (nu(1)',nu(2)',nu(3)') vibrational bands of the (A) over tilde B-1(1)(K'=1)<--(X) over tilde (1)Sigma(g)(+)(0,0,0) perpendicular transition of the (LiOLi)-Li-7-O-16-Li-7 molecule have been rotationally resolved and analyzed to yield effective A',B',C' values. The estimated geometry of the (A) over tilde B-1(1) state does not vary with nu(1)' (symmetric stretch mode), but theta' increases and R' decreases slightly as nu(2)' (bending mode) increases. Extrapolation leads to an estimate for the (0,0,0) state of theta(0)'=105+/-5degrees, R-0'=1.86+/-0.04 Angstrom, and for the potential minimum theta(e)'=102+/-5degrees, R-e'=1.87+/-0.04 Angstrom. The strongly bent nature of the (a) over tilde B-1(1) state is due to promotion of an O-2 p-electron (b(1)) from the strongly ionic, linear Li+O-2Li+ ground state to an a(1) molecular orbital which has Li/Li bonding character. The (A) over tilde B-1(1) state thus has an approximately Li+1/2O-1Li+1/2 charge distribution, so that the ionic bonding is less strong than in the linear ground state, where (from this study and an earlier stimulation-emission pumping study) R-0"=1.611+/-0.003 A. In fact, the Li-Li distance in the (A) over tilde B-1(1) state, similar to3.0 Angstrom, is quite similar to that of the Li-2(+1) ion, so the bonding may be described as that of Li-2(+1) bound ionically to the O-1 ion. (C) 2003 American Institute of Physics.