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Molecular Structure, Thermal, Electronic and Reactivity Propargyl 2-bromoisobutyrate: A Complete Quantum Chemical Study

Year 2022, Volume: 9 Issue: 1, 113 - 122, 31.01.2022
https://doi.org/10.31202/ecjse.949128

Abstract

To predict reactivity and reactive sites on the propargyl 2-bromoisobutyrate molecule, a number of global and local reactivity descriptors have been computed. All calculations have been made through a computational study based on density functional theory (DFT/B3LYP) using a basis set LanL2DZ. The stability of the molecule has been investigated using the natural bond orbital (NBO) analysis. The electronic properties such as HOMO-LUMO energies were determined, and the thermodynamic properties of the title compound were also studied. The electron density-based local reactivity descriptors such as the Fukui functions were calculated to explain the chemical selectivity or reactivity site in the molecule.

References

  • Matyjaszewski K., Coca S., Gaynor S. G., Wei M. and Woodworth B. E., "Zerovalent metals in controlled/“living” radical polymerization", Macromolecules, 1997, 30(23): 7348-7350.
  • Angot S., Murthy K. S., Taton D. and Gnanou Y., "Atom transfer radical polymerization of styrene using a novel octafunctional initiator: synthesis of well-defined polystyrene stars", Macromolecules, 1998, 31(21): 7218-7225.
  • Matyjaszewski K., Coca S., Gaynor S. G., Wei M. and Woodworth B. E., "Controlled radical polymerization in the presence of oxygen", Macromolecules, 1998, 31(17): 5967-5969.
  • Pekdemir M. E., Tukur A. and Coskun M., "Thermal and dielectric investigation of magnetic nanoparticles functionalized with PVC via click chemistry", Polymer Bulletin, 2020: 1-11.
  • Hohenberg P. and Kohn W., "Inhomogeneous electron gas", Physical review, 1964, 136(3B): B864.
  • Finley J. and Stephens P., "Density functional theory calculations of molecular structures and harmonic vibrational frequencies using hybrid density functionals", Journal of Molecular Structure: Theochem, 1995, 357(3): 225-235.
  • Becke A. D., "Thermochemical tests of a kinetic‐energy dependent exchange‐correlation approximation", International Journal of Quantum Chemistry, 1994, 52(S28): 625-632.
  • Frisch A., "Gaussian 09w reference", Wallingford, USA, 25p, 2009.
  • Dennington R., Keith T. and Millam J., "GaussView, version 5", 2009.
  • Koopmans T., "Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms", Physica, 1934, 1(1-6): 104-113.
  • Govindarajan M., Karabacak M., Udayakumar V. and Periandy S., "FT-IR, FT-Raman and UV spectral investigation: Computed frequency estimation analysis and electronic structure calculations on chlorobenzene using HF and DFT", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2012, 88: 37-48.
  • Karakurt T., Dinçer M., Çetin A. and Şekerci M., "Molecular structure and vibrational bands and chemical shift assignments of 4-allyl-5-(2-hydroxyphenyl)-2, 4-dihydro-3H-1, 2, 4-triazole-3-thione by DFT and ab initio HF calculations", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010, 77(1): 189-198.
  • Evecen M., Kara M., Idil O. and Tanak H., "Investigation of antimicrobial activities, DNA interaction, structural and spectroscopic properties of 2-chloro-6-(trifluoromethyl) pyridine", Journal of Molecular Structure, 2017, 1137: 206-215.
  • Schwenke D. W. and Truhlar D. G., "Systematic study of basis set superposition errors in the calculated interaction energy of two HF molecules", The Journal of Chemical Physics, 1985, 82(5): 2418-2426.
  • Gutowski M. and Chal/asiński G., "Critical evaluation of some computational approaches to the problem of basis set superposition error", The Journal of Chemical Physics, 1993, 98(7): 5540-5554.
  • Evecen M. and Tanak H., "DFT quantum chemical studies of (E)-4-Bromo-N-(2-chlorobenzylidene)-aniline", Applied Physics A, 2017, 123(1): 91.
  • Evecen M., "Vibrational spectroscopic studies, HOMO–LUMO, conformational, atomic charge and MEP analyses of ethyl 2-(3-benzoylthioureido)-acetate based on DFT calculations", Journal of Optoelectronics and Advanced Materials, 2016, 18(March-April 2016): 367-377.
  • Kara M., Evecen M. and Özdogan T., "Theoretical investigations on the structural, spectroscopic, electronic and thermodynamic properties of (3-Oxo-3H-benzo [f] chromen-1yl) methyl N, N-dimethylcarbamodithioate-1ex", Materials Science-Poland, 2017, 35(3): 560-575.
  • Sayin K., Karakaş D., Karakuş N., Sayin T. A., Zaim Z. and Kariper S. E., "Spectroscopic investigation, FMOs and NLO analyses of Zn (II) and Ni (II) phenanthroline complexes: A DFT approach", Polyhedron, 2015, 90: 139-146.
  • Fukui K., "Role of frontier orbitals in chemical reactions", science, 1982, 218(4574): 747-754.
  • Karakurt T., Dinçer M., Çukurovalı A. and Yılmaz İ., "Ab initio and semi-empirical computational studies on 5-hydroxy-4-methyl-5, 6-di-pyridin-2-yl-4, 5-dihydro-2H-[1, 2, 4] triazine-3-thione", Journal of Molecular Structure, 2011, 991(1-3): 186-201.
  • Mulliken R., "Electronic population analysis on LCAO‐MO molecular wave functions. IV. Bonding and antibonding in LCAO and valence‐bond theories", The Journal of Chemical Physics, 1955, 23(12): 2343-2346.
  • O'boyle N. M., Tenderholt A. L. and Langner K. M., "Cclib: a library for package‐independent computational chemistry algorithms", Journal of computational chemistry, 2008, 29(5): 839-845.

Propargil 2-bromoizobütiratın Moleküler Yapısı, Termal, Elektronik ve Reaktivitesi: Tam Bir Kuantum Kimyasal Çalışması

Year 2022, Volume: 9 Issue: 1, 113 - 122, 31.01.2022
https://doi.org/10.31202/ecjse.949128

Abstract

Propargil 2 bromoizobutirat molekülü üzerindeki reaktiviteyi ve reaktif bölgeleri tahmin etmek için bir dizi global ve lokal reaktivite tanımlayıcısı hesaplanmıştır. Tüm hesaplamalar, LanL2DZ temel seti kullanılarak yoğunluk fonksiyonel teorisine (DFT/B3LYP) dayalı hesaplamalı çalışma yoluyla yapılmıştır. Molekülün stabilitesi, doğal bağ orbitali (NBO) analizi kullanılarak araştırılmıştır. HOMO-LUMO enerjileri gibi elektronik özellikler belirlendi ve ayrıca başlıktaki bileşiğin termodinamik özellikleri de incelendi. Fukui fonksiyonları gibi elektron yoğunluğuna dayalı lokal reaktivite tanımlayıcıları, moleküldeki kimyasal seçiciliği veya reaktivite bölgesini açıklamak için hesaplandı.

References

  • Matyjaszewski K., Coca S., Gaynor S. G., Wei M. and Woodworth B. E., "Zerovalent metals in controlled/“living” radical polymerization", Macromolecules, 1997, 30(23): 7348-7350.
  • Angot S., Murthy K. S., Taton D. and Gnanou Y., "Atom transfer radical polymerization of styrene using a novel octafunctional initiator: synthesis of well-defined polystyrene stars", Macromolecules, 1998, 31(21): 7218-7225.
  • Matyjaszewski K., Coca S., Gaynor S. G., Wei M. and Woodworth B. E., "Controlled radical polymerization in the presence of oxygen", Macromolecules, 1998, 31(17): 5967-5969.
  • Pekdemir M. E., Tukur A. and Coskun M., "Thermal and dielectric investigation of magnetic nanoparticles functionalized with PVC via click chemistry", Polymer Bulletin, 2020: 1-11.
  • Hohenberg P. and Kohn W., "Inhomogeneous electron gas", Physical review, 1964, 136(3B): B864.
  • Finley J. and Stephens P., "Density functional theory calculations of molecular structures and harmonic vibrational frequencies using hybrid density functionals", Journal of Molecular Structure: Theochem, 1995, 357(3): 225-235.
  • Becke A. D., "Thermochemical tests of a kinetic‐energy dependent exchange‐correlation approximation", International Journal of Quantum Chemistry, 1994, 52(S28): 625-632.
  • Frisch A., "Gaussian 09w reference", Wallingford, USA, 25p, 2009.
  • Dennington R., Keith T. and Millam J., "GaussView, version 5", 2009.
  • Koopmans T., "Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms", Physica, 1934, 1(1-6): 104-113.
  • Govindarajan M., Karabacak M., Udayakumar V. and Periandy S., "FT-IR, FT-Raman and UV spectral investigation: Computed frequency estimation analysis and electronic structure calculations on chlorobenzene using HF and DFT", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2012, 88: 37-48.
  • Karakurt T., Dinçer M., Çetin A. and Şekerci M., "Molecular structure and vibrational bands and chemical shift assignments of 4-allyl-5-(2-hydroxyphenyl)-2, 4-dihydro-3H-1, 2, 4-triazole-3-thione by DFT and ab initio HF calculations", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2010, 77(1): 189-198.
  • Evecen M., Kara M., Idil O. and Tanak H., "Investigation of antimicrobial activities, DNA interaction, structural and spectroscopic properties of 2-chloro-6-(trifluoromethyl) pyridine", Journal of Molecular Structure, 2017, 1137: 206-215.
  • Schwenke D. W. and Truhlar D. G., "Systematic study of basis set superposition errors in the calculated interaction energy of two HF molecules", The Journal of Chemical Physics, 1985, 82(5): 2418-2426.
  • Gutowski M. and Chal/asiński G., "Critical evaluation of some computational approaches to the problem of basis set superposition error", The Journal of Chemical Physics, 1993, 98(7): 5540-5554.
  • Evecen M. and Tanak H., "DFT quantum chemical studies of (E)-4-Bromo-N-(2-chlorobenzylidene)-aniline", Applied Physics A, 2017, 123(1): 91.
  • Evecen M., "Vibrational spectroscopic studies, HOMO–LUMO, conformational, atomic charge and MEP analyses of ethyl 2-(3-benzoylthioureido)-acetate based on DFT calculations", Journal of Optoelectronics and Advanced Materials, 2016, 18(March-April 2016): 367-377.
  • Kara M., Evecen M. and Özdogan T., "Theoretical investigations on the structural, spectroscopic, electronic and thermodynamic properties of (3-Oxo-3H-benzo [f] chromen-1yl) methyl N, N-dimethylcarbamodithioate-1ex", Materials Science-Poland, 2017, 35(3): 560-575.
  • Sayin K., Karakaş D., Karakuş N., Sayin T. A., Zaim Z. and Kariper S. E., "Spectroscopic investigation, FMOs and NLO analyses of Zn (II) and Ni (II) phenanthroline complexes: A DFT approach", Polyhedron, 2015, 90: 139-146.
  • Fukui K., "Role of frontier orbitals in chemical reactions", science, 1982, 218(4574): 747-754.
  • Karakurt T., Dinçer M., Çukurovalı A. and Yılmaz İ., "Ab initio and semi-empirical computational studies on 5-hydroxy-4-methyl-5, 6-di-pyridin-2-yl-4, 5-dihydro-2H-[1, 2, 4] triazine-3-thione", Journal of Molecular Structure, 2011, 991(1-3): 186-201.
  • Mulliken R., "Electronic population analysis on LCAO‐MO molecular wave functions. IV. Bonding and antibonding in LCAO and valence‐bond theories", The Journal of Chemical Physics, 1955, 23(12): 2343-2346.
  • O'boyle N. M., Tenderholt A. L. and Langner K. M., "Cclib: a library for package‐independent computational chemistry algorithms", Journal of computational chemistry, 2008, 29(5): 839-845.
There are 23 citations in total.

Details

Primary Language Turkish
Subjects Engineering
Journal Section Makaleler
Authors

Seda Hekim 0000-0003-1932-6978

Mustafa Ersin Pekdemir 0000-0002-4979-1777

Publication Date January 31, 2022
Submission Date June 7, 2021
Acceptance Date July 8, 2021
Published in Issue Year 2022 Volume: 9 Issue: 1

Cite

IEEE S. Hekim and M. E. Pekdemir, “Propargil 2-bromoizobütiratın Moleküler Yapısı, Termal, Elektronik ve Reaktivitesi: Tam Bir Kuantum Kimyasal Çalışması”, ECJSE, vol. 9, no. 1, pp. 113–122, 2022, doi: 10.31202/ecjse.949128.