Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3

Cooper, Jason K.; Grant, Christian D.; Zhang, Jin Z.

doi:10.2147/RTC.S36686

Title: Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3

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Abstract

The vertical and adiabatic ionization potential (IP_V and IP_A) and vertical electron affinity (EA_V) for six explosives (RDX, HMX, TNT, PETN, HMTD, and TATP) have been studied by ab initio computational methods. The IPV was calculated using MP2 and CBS-QB3 while the IP_A was calculated with B3LYP, CAM-B3LYP, ω B97XD, B2PLYP, and MP2. RDX and TNT IP_A’s were also reported using CBS -QB3. Excluding results by CBS-QB3, B3LYP and B2PLYPD provided superior and more consistent results for calculating the IP. The EA_V were calculated using the same methods however B3LYP performed the worst in this case with MP2 and B2PLYPD predicting values closest to those made by CBS-QB3, which was used a reference due to lacking experimental data. Basis set effects were evaluated using 6- 31+G(d,p), 6-311+G(d,p), and 6-311+(3df,2p) for both IP and EA. 6-31+G(d,p) gave satisfactory results for calculating both IP however 6-311+G(3df,2p) had improved results in calculating the EA. The four nitro containing compounds had exothermic reduction potentials while the peroxides were unfavorable. Additionally, it was seen that RDX, HMX, TATP and HMTD were unstable in their reduced forms. Results are aimed to assist detection and screening methods.

Authors:

Cooper, Jason K. ^[1]; Grant, Christian D. ^[2]; Zhang, Jin Z. ^[1]

Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Chemical Sciences Division

Publication Date:: Fri Jul 20 00:00:00 EDT 2012

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1343013

Report Number(s):: LLNL-JRNL-566174
Journal ID: ISSN 2230-410X

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: Reports in Theoretical Chemistry

Additional Journal Information:: Journal Volume: 2012; Journal Issue: 1; Journal ID: ISSN 2230-410X

Publisher:: Dovepress

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats


                    Cooper, Jason K., Grant, Christian D., and Zhang, Jin Z. Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3.  United States: N. p., 2012. 
Web.  doi:10.2147/RTC.S36686.

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                    Cooper, Jason K., Grant, Christian D., & Zhang, Jin Z. Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3.  United States.  https://doi.org/10.2147/RTC.S36686

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                    Cooper, Jason K., Grant, Christian D., and Zhang, Jin Z. Fri .  
"Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3".  United States.  https://doi.org/10.2147/RTC.S36686.  https://www.osti.gov/servlets/purl/1343013.

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@article{osti_1343013,

  title        = {Ionization potential and electron affinity for six common explosive compounds by DFT, MP2, and CBS-QB3},

  author       = {Cooper, Jason K. and Grant, Christian D. and Zhang, Jin Z.},

  abstractNote = {The vertical and adiabatic ionization potential (IPV and IPA) and vertical electron affinity (EAV) for six explosives (RDX, HMX, TNT, PETN, HMTD, and TATP) have been studied by ab initio computational methods. The IPV was calculated using MP2 and CBS-QB3 while the IPA was calculated with B3LYP, CAM-B3LYP, ω B97XD, B2PLYP, and MP2. RDX and TNT IPA’s were also reported using CBS -QB3. Excluding results by CBS-QB3, B3LYP and B2PLYPD provided superior and more consistent results for calculating the IP. The EAV were calculated using the same methods however B3LYP performed the worst in this case with MP2 and B2PLYPD predicting values closest to those made by CBS-QB3, which was used a reference due to lacking experimental data. Basis set effects were evaluated using 6- 31+G(d,p), 6-311+G(d,p), and 6-311+(3df,2p) for both IP and EA. 6-31+G(d,p) gave satisfactory results for calculating both IP however 6-311+G(3df,2p) had improved results in calculating the EA. The four nitro containing compounds had exothermic reduction potentials while the peroxides were unfavorable. Additionally, it was seen that RDX, HMX, TATP and HMTD were unstable in their reduced forms. Results are aimed to assist detection and screening methods.},

  doi          = {10.2147/RTC.S36686},

  journal      = {Reports in Theoretical Chemistry},

  number       = 1,

  volume       = 2012,

  place        = {United States},

  year         = {Fri Jul 20 00:00:00 EDT 2012},

  month        = {Fri Jul 20 00:00:00 EDT 2012}

}

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