摘要
运用Materials Studio程序和广义梯度泛函(GGA)PW91方法,在增加了极化函数的双数值基组(DNP)精度下对3,6-二氨基均四嗪(DATz)、3,6-二肼基均四嗪(DHT)和3,6-二叠氮均四嗪(DIAT)气相分子结构和晶体结构进行了全优化,进行了能带分析、晶体态密度(DOS)及局域态密度(PDOS)计算。讨论了其热力学函数随温度变化规律。能带分析得到这三种四嗪衍生物的稳定性次序:DIAT<DHT<DATz;态密度(DOS)及局域态密度(PDOS)分析及Wiberg键级分析得到DATz、DHT和DIAT的主要反应活性位置为四嗪环上的N原子。对上述三种化合物分子晶体的振动分析结果表明:其热力学函数(Sθm、Cθp,m、Hθm和Gθm)与温度T近似有线性关系。随T升高,Sθm、Cθp,m和Hθm逐渐增大,而Gθm逐渐减小。
The gas phase molecular structures and crystal structures of 3,6-diamino-1,2,4,5-tetrazine（DATz）,3,6-dihydrazino-1,2,4,5-tetrazine（DHT） and 3,6-diazido-1,2,4,5-tetrazine（DIAT） were full optimized at the GGA-PW91/DNP level with Materials Studio Program.The energy band,density of state（DOS） and part density of state（PDOS） were calculated.The change rule of the thermodynamic functions with temperature were discussed.The results show that the stability of three tetrazine derivatives obtained by the energy band increases in the order DHTDATzDIAT.The active site in main reaction of DATz,DHT and DIAT obtained by analysis of DOS,PDOS and Wiberg bond is N atom on tetrazine ring.The crystal vibration analyses infer that their thermodynamic functions（Sθ m、Cθp,m 、Hθm and Gθm）display a nearly linear correlation with temperature.With the temperature increasing,Sθ m、Cθp,m and Hθm gradually increase,whereas Gθm gradually decrease.
出处
《含能材料》
EI
CAS
CSCD
北大核心
2013年第3期281-288,共8页
Chinese Journal of Energetic Materials
基金
国家自然科学基金委-中国工程物理研究院联合基金(NSAF10776002)
教育部新世纪优秀人才支持计划项目(NCET-09-0051)
关键词
物理化学
双取代四嗪
能带分析
态密度分析
热力学计算
physical chemistry
bi-substituted tetrazine
band energy analysis
density of state
thermodynamic calculation
