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Reactivity of N-NO2 Bonds in Nitramines: Bond Dissociation and Bond Disproportionation Approach
Authors: Friedl Zdeněk | Zeman Svatopluk
Year: 2007
Type of publication: článek ve sborníku
Name of source: Theory & Practice of Energetic Materials
Publisher name: Science Press
Place: Beijing
Page from-to: 410-417
Titles:
Language Name Abstract Keywords
cze Reaktivita N-NO2 vazeb v nitraminech: přístup přes disociaci vazby a disproporcionaci vazby Homolytická disociace of N?NO2 vazby je primárním štěpením nitraminů v iniciaci teplem, nárazem, šokem a elektrickou jiskrou. Tato disociace je nejčastěji charakterizována homolytickou vazebnou disociační energií BDE(N?NO2). Teoretický výpočet of BDE hodnot je podstatně ovliněn nedostatečným ošetřením elektronové korelace. Nedávno byla navržena alternativní metoda pro překonání tohoto nedostatku ? přistup separace vazby je popsán isodesmickou reakcí RN?NO2 + SN-H  RN?H + SN-NO2, kde SN-NO2 je standardní nitramin (NPI). Tento typ virtuální symetrické chemické rovnováhy, charakterizované jako vazebné disproporciační reakce, neodmyslitelně vyruší elektronový korelační efekt související s homolytickou disociací vazby vazebná disociační energie;, vazebná disproporcionační energie; nitraminy; detonační rychlost;, odštěpení nitroskupiny;, iniciace
eng Reactivity of N-NO2 Bonds in Nitramines: Bond Dissociation and Bond Disproportionation Approach The homolytic dissociation of N?NO2 bond represents the primary fission process of nitramines under thermal, impact, shock and electric spark initiation stimuli. The N?NO2 bond fission is mostly characterized by homolytic bond dissociation energies BDE(N?NO2). The theoretical calculations of BDE energies are substantially influenced from inadequate treatment of electron correlation. Recently the alternative method was suggested to overcome this substantial drawback ? the bond separation approach described by an isodesmic reaction RN?NO2 + SN-H  RN?H + SN-NO2 where SN-NO2 is a standard nitramine (NPI). This type of virtual symmetrical chemical equilibria, characterized as bond disproportionation reactions, inherently cancel the electron correlation effects accompanying homolytic bond dissociation. The bond disproportionation energies DISP(N-NO2) and bond dissociation energies BDE(N?NO2) were evaluated for 20 nitramines at ab initio DFT B3LYP/6-311+G(d,p) level and correlated with their detonation velocities D. It is shown that DISP approach can be used seemingly with advantage over BDE energies for unambiguous description of molecular structural dependence of detonation. However, semilogarithmic analysis of these two relationships leads to finding that the resulting correlations of ln D values with DISP(N?NO2) or BDE(N?NO2) values remind analogous LFER relationships between the rate and Hammett substituent constants. bond dissociation energy bond disproportionation energy; nitramines; detonation velocity; split off nitro groups, initiation

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