Yüksek Enerjili Patlayıcı Moleküllerin Yapısal, Spektroskopik ve Elektronik Özelliklerinin Ab-initio Çalışması: YFT/TD-YFT Hesaplamaları

Year 2024, Volume: 14 Issue: 3, 1081 - 1095, 15.09.2024

Yavuz Ekincioğlu , Abdullah Kepceoğlu

https://doi.org/10.31466/kfbd.1416995

Abstract

Bu araştırma, FOX-7 ve nitroguanidin moleküllerinin temel durum geometrisini ve moleküler özelliklerini incelemekte olup özellikle spektroskopik ve elektronik karakteristiklerine odaklanmaktadır. İlk olarak, her molekülün konformasyonel uzayı moleküler mekanik hesaplamalar kullanılarak sistemli bir şekilde tarandı ve her molekül için en olası konformer yapı elde edildi. Daha sonra, moleküllerin geometri optimizasyonları, Becke'nin üç parametreli hibrid-değişim fonksiyonu içeren ab initio yoğunluk fonksiyonel teorisi (DFT) kullanılarak gerçekleştirildi. Bu, Lee–Yang–Parr korelasyon fonksiyonelini (B3LYP) içeren yöntem ve standart 6-311++G(d,p) baz setini içermektedir. Teorik olarak belirlenen geometrik parametreler, optimize edilmiş yapıdan elde edilen deneysel değerlerle karşılaştırılarak, her iki molekülün yapısal özelliklerinin doğrulanmasını sağlamıştır. Ayrıca, her iki molekülün kararlılık ve reaktivite özellikleri HOMO-LUMO enerjileri açısından tahmin edilmiştir. Genel olarak, bu çalışma, FOX-7 ve nitroguanidin'in temel durum geometrisi, moleküler yapısı ve spektroskopik davranışının kapsamlı bir anlayışına katkıda bulunmakta olup, bilim ve teknolojinin çeşitli alanlarında potansiyel uygulamalar için yol açmaktadır.

Keywords

YFT, Moleküler Yapı, HOMO, LUMO, Spektroskopik Özellikler, FOX-7, Nitroguanidin

Ab-initio Study of Structural, Spectroscopic and Electronic Properties of High Energy Explosive Molecules: DFT/TD-DFT Calculations

Abstract

This research explores the ground state geometry and molecular properties of FOX-7 and nitroguanidine molecules, with a focus on their spectroscopic and electronic characteristics. Initially, the conformational space of each molecule was systematically scanned using molecular mechanic calculations and the most probable conformer structure was obtained for each molecule. Subsequently, geometry optimizations of molecules were conducted by using ab initio density functional theory (DFT) with Becke’s three-parameter hybrid-exchange functional, which combines the Lee–Yang–Parr correlation functional (B3LYP) method, and the standard 6-311++G(d,p) basis set. The theoretically determined geometrical parameters from optimized structure and experimental values available in the literature were compared, providing validation for the structural properties of both molecules. Furthermore, the stability and reactivity properties of both molecules are estimated in terms of HOMO-LUMO energies. Overall, this study contributes to a comprehensive understanding of the ground state geometry, molecular structure, and spectroscopic behavior of FOX-7 and nitroguanidine, paving the way for potential applications in various fields of science and technology.

Keywords

DFT, Molecular Structures, HOMO, LUMO, Spectroscopic Properties, FOX-7, Nitroguanidine

References

• Agrawal, J. P., (2010). High energy materials: propellants, explosives and pyrotechnics: John Wiley & Sons.
• Chavez, D., Hill, L., Hiskey, M., and Kinkead, S., (2000). Preparation and explosive properties of azo-and azoxy-furazans. Journal of Energetic Materials, 18(2-3), 219-236.
• Chu, G.-b., Xi, T., Wang, S.-y., Shui, M., Yan, Y.-h., Lv, G.-q., and Tan, F., (2023). Recent progress in research on the dynamic process of high-energy explosives through pump-probe experiments at high-intensity laser facilities. Energetic Materials Frontiers.
• Cotton, F. A., Wilkinson, G., Murillo, C. A., and Bochmann, M. (1999). Advanced inorganic chemistry: John Wiley & Sons.
• De Silva, I. C., De Silva, R. M., and De Silva, K. N., (2005). Investigations of nonlinear optical (NLO) properties of Fe, Ru and Os organometallic complexes using high accuracy density functional theory (DFT) calculations. Journal of Molecular Structure: THEOCHEM, 728(1-3), 141-145.
• Dixon, D. A., and Matsuzawa, N., (1994). Density functional study of the structures and nonlinear optical properties of urea. The Journal of Physical Chemistry, 98(15), 3967-3977.
• Ekincioğlu, Y., Kılıç, H. Ş., and Dereli, Ö., (2021). DFT Study of Conformational Analysis, Molecular Structure and Properties of para-, meta-and ortho 4-Methoxyphenyl Piperazine Isomers. Brazilian Journal of Physics, 51(4), 958-968.
• Fleming, I. (1976). Frontier orbitals and organic chemical reactions. (No Title).
• Frisch, M., Trucks, G., Schlegel, H., Scuseria, G., Robb, M., Cheeseman, J., and Petersson, G., (2009). 09, Revision D. 01, Gaussian. Inc., Wallingford, CT.
• Ghanta, S. (2016). Theoretically predicted Fox-7 based new high energy density molecules. Journal of Molecular Structure, 1118, 28-33.
• Ghanta, S., (2023). Design of derivatives of FOX-7-based new four-member heterocyclic insensitive high energy density molecules: a theoretical prospectives. Journal of Molecular Modeling, 29(1), 18.
• Halgren, T. A., (1996). Merck molecular force field. I. Basis, form, scope, parameterization, and performance of MMFF94. Journal of computational chemistry, 17(5‐6), 490-519.
• He, P. Zhang, J.-G., Wang, K., Yin, X., Jin, X., and Zhang, T.-L., (2015). Extensive theoretical studies on two new members of the FOX-7 family: 5-(dinitromethylene)-1, 4-dinitramino-tetrazole and 1, 1′-dinitro-4, 4′-diamino-5, 5′-bitetrazole as energetic compounds. Physical Chemistry Chemical Physics, 17(8), 5840-5848.
• Improta, R., and Barone, V., (2004). Absorption and fluorescence spectra of uracil in the gas phase and in aqueous solution: A TD-DFT quantum mechanical study. Journal of the American Chemical Society, 126(44), 14320-14321.
• Jeffrey, G. A., and Jeffrey, G. A., (1997). An introduction to hydrogen bonding: Oxford university press New York. 12
• Jeong, K., Jeon, Y., and Kwon, S., (2017). Assessment of various DFT, DFT-D, and MP2 methods for studying FOX-7 detonation properties. Journal of Molecular Modeling, 23, 1-6.
• Karelson, M., Lobanov, V. S., and Katritzky, A. R., (1996). Quantum-chemical descriptors in QSAR/QSPR studies. Chemical reviews, 96(3), 1027-1044.
• Klapötke, T. M., (2022). Chemistry of high-energy materials: Walter de Gruyter GmbH & Co KG.
• Koch, E. C., (2019). Insensitive high explosives: III. Nitroguanidine–synthesis–structure–spectroscopy–sensitiveness. Propellants, Explosives, Pyrotechnics, 44(3), 267-292.
• Koopmans, T., (1934). About the assignment of wave functions and eigenvalues to the individual electrons of an atom. Physica, 1(1-6), 104-113.
• Kuklja, M., Rashkeev, S., and Zerilli, F., (2004). Ab initio Calculations of the Electronic Structure of 1, 1‐Diamino‐2, 2‐Dinitroethylene. Paper presented at the AIP Conference Proceedings.
• Manna, M. S., Das, C. K., and Ghanta, S., (2021). Design of CHNO based new hetero-cyclic high energy density molecules: a theoretical survey. Structural Chemistry, 32, 1095-1104.
• Mondal, T., Saritha, B., Ghanta, S., Roy, T., Mahapatra, S., and Prasad, M. D., (2009). On some strategies to design new high energy density molecules. Journal of Molecular Structure: THEOCHEM, 897(1-3), 42-47.
• O'boyle, N. M., Tenderholt, A. L., and Langner, K. M., (2008). Cclib: a library for package‐independent computational chemistry algorithms. Journal of computational chemistry, 29(5), 839-845.
• Östmark, H., Langlet, A., Bergman, H., Wingborg, N., Wellmar, U., and Bemm, U., (1998). FOX-7–A new explosive with low sensitivity and high performance. Paper presented at the The 11th International Detonation Symposium, Colorado, USA.
• Prasad, P. N. and Williams, D. J., (1991). Introduction to nonlinear optical effects in molecules and polymers: Wiley New York. 1.
• Pravica, M., Liu, Y., Robinson, J., Velisavljevic, N., Liu, Z., and Galley, M., (2012). A high-pressure far-and mid-infrared study of 1, 1-diamino-2, 2-dinitroethylene. Journal of Applied Physics, 111(10).
• Prendergast, R., (2018). A Solid-State Theoretical and Experimental Analysis of Nitroguanidine and Gunshot Residues. Syracuse University,
• Shao, Y., Molnar, L., Jung, Y., Kussmann, J., Ochsenfeld, C., Brown, S., and O’Neill, D., (2006). Spartan’08, Wavefunction, Inc. Irvine, CA. Phys. Chem. Chem. Phys, 8, 3172-3191.
• Sorescu, D. C., Boatz, J. A., and Thompson, D. L., (2001). Classical and quantum-mechanical studies of crystalline FOX-7 (1, 1-diamino-2, 2-dinitroethylene). The Journal of Physical Chemistry A, 105(20), 5010-5021.
• Sorescu, D. C., Boatz, J. A., and Thompson, D. L., (2003). First-principles calculations of the adsorption of nitromethane and 1, 1-diamino-2, 2-dinitroethylene (FOX-7) molecules on the Al (111) surface. The Journal of Physical Chemistry B, 107(34), 8953-8964.
• Sun, Q., Zhang, Y., Xu, K., Ren, Z., Song, J., and Zhao, F., (2015). Studies on thermodynamic properties of FOX-7 and its five closed-loop derivatives. Journal of Chemical & Engineering Data, 60(7), 2057-2061.
• Taylor, D. E., Rob, F., Rice, B. M., Podeszwa, R., and Szalewicz, K., (2011). A molecular dynamics study of 1, 1-diamino-2, 2-dinitroethylene (FOX-7) crystal using a symmetry adapted perturbation theory-based intermolecular force field. Physical Chemistry Chemical Physics, 13(37), 16629-16636.
• Vijayaraj, R., Subramanian, V., and Chattaraj, P. (2009). Comparison of global reactivity descriptors calculated using various density functionals: a QSAR perspective. Journal of chemical theory and computation, 5(10), 2744-2753.