${\mathrm{D}}_{2}$ molecules, excited by linearly cross-polarized femtosecond extreme ultraviolet (XUV) and near-infrared (NIR) light pulses, reveal highly structured ${\mathrm{D}}^{+}$ ion fragment momenta and angular distributions that originate from two different four-step dissociative ionization pathways after four-photon absorption (one XUV $+$ three NIR). We show that, even for very low dissociation kinetic energy release $\ensuremath{\le}$ 240 meV, specific electronic excitation pathways can be identified and isolated in the final ion momentum distributions. With the aid of ab initio electronic structure and time-dependent Schr\"odinger equation calculations, angular momentum, energy, and parity conservation are used to identify the excited neutral molecular states and molecular orientations relative to the polarization vectors in these different photoexcitation and dissociation sequences of the neutral ${\mathrm{D}}_{2}$ molecule and its ${\mathrm{D}}_{2}^{+}$ cation. In one sequential photodissociation pathway, molecules aligned along either of the two light polarization vectors are excluded, while another pathway selects molecules aligned parallel to the light propagation direction. The evolution of the nuclear wave packet on the intermediate $B{\phantom{\rule{0.16em}{0ex}}}^{1}{\mathrm{\ensuremath{\Sigma}}}_{u}^{+}$ electronic state of the neutral ${\mathrm{D}}_{2}$ molecule is also probed in real time.
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