Highlights1. The molecular geometry, AIM analysis, electrostatic and IBSI, PDA and NBO properties of the 34DNP and DNPP molecules were analysed.2. The tilted -NO2 in the isolated pyrazole ring is favorable for increasing the O-O bond character in -NO2 and leads to less favorable bonding with the pyrazole ring.3. The dinitropyrazole ring fusion provides coplanarity to -NO2 with the pyrazole ring and less steric interaction with the molecule.4. The isolated pyrazole ring provides higher acidity to the attached hydrogen than the fused pyrazole ring.