Safety plays an important role in determining the applicability of energetic compounds,and the bond dissociation enthalpy(BDE)of the“trigger bond”X-NO_(2) provides useful information to evaluate various safety prope...Safety plays an important role in determining the applicability of energetic compounds,and the bond dissociation enthalpy(BDE)of the“trigger bond”X-NO_(2) provides useful information to evaluate various safety properties.Accurate and rapid calculation of the BDE of X-NO_(2) is of great significance to perform the high-throughput design of energetic compounds,which becomes an increasingly popular means of materials design.We conduct a benchmark BDE calculation for 44 X-NO_(2) samples extracted from the iBond database,with the accuracies of 55 quantum chemistry calculation levels evaluated by the experimentally measured values.Only four levels have the global mean-absolute deviation(MAD)less than 10 kJ/mol,but no calculation level can achieve that all the local MADs of each category less than 10 kJ/mol.We propose a simple correction strategy for the original calculation deviations,and apply it to 30 calculation levels screened out through a series of accuracy assessments and obtain the corrected MAD<6 kJ/mol in some cases.We define a normalized time-cost(NTC)to evaluate the time-cost of each calculation level,and confirm that PBE0-D3/6-31G^(**)(MAD=6.4 kJ/mol,NTC?0.8)works the best for most cases,followed by M062X/6-31g^(**),M062X/6-311g^(**)andɷB97XD/6-311g^(**),based on an insight into the accuracy-cost trade.The present work provides an accurate and fast solution for calculating XNO_(2) BDE via quantum chemical methods,and is expected to be beneficial to enhance the safety prediction efficiency of energetic compounds.展开更多
基金the support of the Science Challenge Project(TZ-2018004)。
文摘Safety plays an important role in determining the applicability of energetic compounds,and the bond dissociation enthalpy(BDE)of the“trigger bond”X-NO_(2) provides useful information to evaluate various safety properties.Accurate and rapid calculation of the BDE of X-NO_(2) is of great significance to perform the high-throughput design of energetic compounds,which becomes an increasingly popular means of materials design.We conduct a benchmark BDE calculation for 44 X-NO_(2) samples extracted from the iBond database,with the accuracies of 55 quantum chemistry calculation levels evaluated by the experimentally measured values.Only four levels have the global mean-absolute deviation(MAD)less than 10 kJ/mol,but no calculation level can achieve that all the local MADs of each category less than 10 kJ/mol.We propose a simple correction strategy for the original calculation deviations,and apply it to 30 calculation levels screened out through a series of accuracy assessments and obtain the corrected MAD<6 kJ/mol in some cases.We define a normalized time-cost(NTC)to evaluate the time-cost of each calculation level,and confirm that PBE0-D3/6-31G^(**)(MAD=6.4 kJ/mol,NTC?0.8)works the best for most cases,followed by M062X/6-31g^(**),M062X/6-311g^(**)andɷB97XD/6-311g^(**),based on an insight into the accuracy-cost trade.The present work provides an accurate and fast solution for calculating XNO_(2) BDE via quantum chemical methods,and is expected to be beneficial to enhance the safety prediction efficiency of energetic compounds.
