Recent advent of diverse chemical entities necessitates a re-evaluation of chemical bond concepts, underscoring the importance of experimental evidence. Our prior study introduced a general methodology, termed Core Differential Fourier Synthesis (CDFS), for mapping the distribution of valence electron density (VED) in crystalline substances within real space. In this study, we directly compare the VED distributions obtained through CDFS with those derived from high-accuracy theoretical calculation using long-range corrected density functional theory, which quantitatively reproduces accurate orbital energies. This comparison serves to demonstrate the precision of the CDFS in replicating complex details. The VED patterns observed experimentally exhibited detailed structures and phases of wave functions indicative of sp3 hybrid orbitals, closely aligning with theoretical predictions. This alignment underscores the utility of our approach in gathering quantum chemical data experimentally, a crucial step for discussing the chemical properties, such as reaction mechanisms.