1-fluoro-pentane-2,4-dione (monofluoroacetylacetone, MFAA) is an asymmetric β-diketone with a strong intramolecular hydrogen bond similar to acetylacetone (AA) and its fluorinated analogs 1,1,1trifluoro-(TFAA), and 1,1,1,5,5,5-hexafluoroacetylacetone (HFAA). The presence of a fluorine atom in MFAA has the potential to open an HF elimination channel in its gas-phase photochemistry motivating this study of MFAA hydrogen bonding by computer modeling using Density Functional Theory (DFT). As a context, we also report DFT modeling of AA and selected fluorinated acetylacetones: 1,1-difluoropentane-2,4-dione (difluoroacetylacetone, DFAA), TFAA, and HFAA. The most stable molecular structure for all three asymmetric β-diketones (MFAA, DFAA and TFAA) is the isomer with the fluoromethyl group proximal to the carbonyl carbon; in comparison to the proton transfer isomer, which has the fluoromethyl group proximal to the hydroxyl carbon, the carbonyl isomer is lower in energy by 5.1-5.5 kJ mol-1 (B3LYP/cc-pVTZ) and 2.1-3.7 kJ mol-1 (MP2/Aug-cc-pVTZ). We also report hydrogen bond strengths, barriers to proton transfer interconversion and barriers to rotation of the methyl/fluoromethyl groups. Our study, the first to report molecular structure information on MFAA and DFAA, indicates that the most stable chelated isomer of MFAA is not the structure with the strongest hydrogen bond as conventionally determined. Our modeling also reveals a coupling between proton transfer isomerization and methyl group rotation, and an unexpected double-minimum potential for the rotation of the fluoromethyl group of MFAA.