Theoretical Investigation of the Structures and Energetics of (MX)-Ethanol Complexes in the Gas Phase

Year 2023, Volume: 10 Issue: 1, 47 - 54, 28.02.2023

Ahmed M. Sadoon

https://doi.org/10.18596/jotcsa.1146250

Cited By: 1

Abstract

The structures and energy of alkali halide salt (MX) complexes with ethanol have been investigated in this work. The core of this study is to explore the effect of ion size on the interactions between solvent and solute. LiF and KBr as monovalent salts with different sizes of inion and cation have been chosen to explore this difference in addition to various physical properties. Three complexes of each LiF and KBr with ethanol taking the formula MX(CH3CH2OH)n (n=1-3), were studied. Ab-initio calculations have been performed to optimize the chemical structures of these complexes and explore the possible structures, isomers, and their corresponding IR spectra using Density functional theory (DFT/ B3LYP). 6-311G** were chosen as basis sets for these calculations. The geometry evaluations, energy searches, vibrational frequency calculations, and each complex's binding energy were also theoretically extracted in this study. The minimum energy structures were calculated, and different isomers were found. The presence of Ionic hydrogen bonds (IHBs) was observed and proposed to be the main binding between the MX salt and ethanol. Also, the infrared vibrational bands in the OH stretching region were recorded for the minimum structures, and the determined red-shift was at about 400 cm-1. In addition, the binding energy calculations found a gradual rise in the BE value with every additional ethanol molecule added to MX salt.

Keywords

Infrared Spectroscopy, DFT, Alkaline metal, Ethanol.

Supporting Institution

University of Mosul

Thanks

The author is grateful to the University of Mosul and the Chemistry department at the College of Education for pure sciences for their support and funding this work

References

• 1. Satchell DPN. Ions in solution: Basic principles of chemical interactions. Endeavour [Internet]. 1988 Jan [cited 2022 Nov 27];12(4):195.
• 2. Marcus Y. Ions in Solution and their Solvation: Marcus/Ions in Solution and their Solvation [Internet]. Hoboken, NJ: John Wiley & Sons, Inc; 2015 [cited 2022 Nov 27].
• 3. Friedman HaroldL. Ionic hydration in chemistry and biophysics. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry [Internet]. 1982 Jan [cited 2022 Nov 27];131:407–8.
• 4. Marcus Y. Effect of ions on the structure of water. Pure and Applied Chemistry [Internet]. 2010 Jun 19 [cited 2022 Nov 27];82(10):1889–99.
• 5. Moelbert S, Normand B, De Los Rios P. Kosmotropes and chaotropes: modelling preferential exclusion, binding and aggregate stability. Biophysical Chemistry [Internet]. 2004 Dec [cited 2022 Nov 27];112(1):45–57.
• 6. Aigueperse J, Mollard P, Devilliers D, Chemla M, Faron R, Romano R, et al. Fluorine Compounds, Inorganic. In: Wiley-VCH Verlag GmbH & Co. KGaA, editor. Ullmann’s Encyclopedia of Industrial Chemistry [Internet]. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA; 2000 [cited 2022 Nov 27]. p. a11_307.
• 7. Zheng Y, Song W, Mo W ting, Zhou L, Liu JW. Lithium fluoride recovery from cathode material of spent lithium-ion battery. RSC Adv [Internet]. 2018 [cited 2022 Nov 27];8(16):8990–8.
• 8. Andeen C, Fontanella J, Schuele D. Low-Frequency Dielectric Constant of LiF, NaF, NaCl, NaBr, KCl, and KBr by the Method of Substitution. Phys Rev B [Internet]. 1970 Dec 15 [cited 2022 Nov 27];2(12):5068–73.
• 9. McGregor DS, Bellinger SL, Shultis JK. Present status of microstructured semiconductor neutron detectors. Journal of Crystal Growth [Internet]. 2013 Sep [cited 2022 Nov 27];379:99–110.
• 10. De Lahunta A, Glass E, Kent M. Veterinary Neuroanatomy and Clinical Neurology [Internet]. Elsevier; 2009 [cited 2022 Nov 27].
• 11. Alpert NL, Keiser WE., Szymanski HA. IR: Theory and Practice of Infrared Spectroscopy. Cham: Springer International Publishing; 2012. 381 p.
• 12. Anchell S. The Film Developing Cookbook [Internet]. 1st ed. Routledge; 1998 [cited 2022 Nov 27].
• 13. Tandy J, Feng C, Boatwright A, Sarma G, Sadoon AM, Shirley A, et al. Communication: Infrared spectroscopy of salt-water complexes. The Journal of Chemical Physics [Internet]. 2016 Mar 28 [cited 2022 Nov 27];144(12):121103.
• 14. Sadoon AM, Sarma G, Cunningham EM, Tandy J, Hanson-Heine MWD, Besley NA, et al. Infrared Spectroscopy of NaCl(CH 3 OH) n Complexes in Helium Nanodroplets. J Phys Chem A [Internet]. 2016 Oct 20 [cited 2022 Nov 27];120(41):8085–92.
• 15. Li RZ, Liu CW, Gao YQ, Jiang H, Xu HG, Zheng WJ. Microsolvation of LiI and CsI in Water: Anion Photoelectron Spectroscopy and ab initio Calculations. J Am Chem Soc [Internet]. 2013 Apr 3 [cited 2022 Nov 27];135(13):5190–9.
• 16. Mizoguchi A, Ohshima Y, Endo Y. The study for the incipient solvation process of NaCl in water: The observation of the NaCl–(H 2 O) n ( n = 1, 2, and 3) complexes using Fourier-transform microwave spectroscopy. The Journal of Chemical Physics [Internet]. 2011 Aug 14 [cited 2022 Nov 27];135(6):064307.
• 17. Doll K, Schön JC, Jansen M. Ab initio energy landscape of LiF clusters. The Journal of Chemical Physics [Internet]. 2010 Jul 14 [cited 2022 Nov 27];133(2):024107.
• 18. Umer M, Kopp WA, Leonhard K. Efficient yet accurate approximations for ab initio calculations of alcohol cluster thermochemistry. The Journal of Chemical Physics [Internet]. 2015 Dec 7 [cited 2022 Nov 27];143(21):214306.
• 19. Sangoro J, Cosby T, Kremer F. Rotational and Translational Diffusion in Ionic Liquids. In: Paluch M, editor. Dielectric Properties of Ionic Liquids [Internet]. Cham: Springer International Publishing; 2016 [cited 2022 Nov 27]. p. 29–51. (Advances in Dielectrics).
• 20. Nancollas GH. The thermodynamics of metal-complex and ion-pair formation. Coordination Chemistry Reviews [Internet]. 1970 Dec [cited 2022 Nov 27];5(4):379–415.
• 21. Meot-Ner (Mautner) M. Update 1 of: Strong Ionic Hydrogen Bonds. Chem Rev [Internet]. 2012 Oct 10 [cited 2022 Nov 27];112(10):PR22–103.
• 22. Eisenberg B. Ionic Interactions Are Everywhere. Physiology [Internet]. 2013 Jan [cited 2022 Nov 27];28(1):28–38.
• 23. Zhurko G, Zhurko D. Chemcraft-graphical software for visualization of quantum chemistry computations [Internet]. 2016.
• 24. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et al. Gaussian 03, Revision C.02 [Internet]. Gaussian, Inc.; 2004.
• 25. Schuchardt KL, Didier BT, Elsethagen T, Sun L, Gurumoorthi V, Chase J, et al. Basis Set Exchange: A Community Database for Computational Sciences. J Chem Inf Model [Internet]. 2007 May 1 [cited 2022 Nov 27];47(3):1045–52.
• 26. Johnson R. Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database 101 [Internet]. National Institute of Standards and Technology; 2002 [cited 2022 Nov 27].
• 27. Cabarcos OM, Weinheimer CJ, Martı́nez TJ, Lisy JM. The solvation of chloride by methanol—surface versus interior cluster ion states. The Journal of Chemical Physics [Internet]. 1999 May 15 [cited 2022 Nov 27];110(19):9516–26.
• 28. Beck JP, Lisy JM. Cooperatively Enhanced Ionic Hydrogen Bonds in Cl − (CH 3 OH) 1−3 Ar Clusters. J Phys Chem A [Internet]. 2010 Sep 23 [cited 2022 Nov 27];114(37):10011–5. .