Time Dependent- Density Functional Theory calculations on frequency-dependent photophysical properties of 2, 3-diphenylcyclopropenone
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Time Dependent Density Functional Theory (TD-DFT/B3LYP/6-31G*) calculations have been performed on the optimized structure of 2, 3-diphenylcyclopropenone (DPCP) in the UV region of the spectra; giving energies, oscillator strength, dipole moment, µ and polarizability, α in solvents of different polarities. The study was also extended to the number of transitions, frontier orbital energy gaps (ELUMO - EHOMO) analysis of this strained ring donor - acceptor (D-A) molecular system to calculate its ionization potential (I), electron affinity (EA) and global hardness (η) in the solvent of choice. This aids in understanding the relationship between the structure and properties of this molecule.TD-DFT/B3LYP/6-31G* calculation results, when compared with the reported experimental studies results of the solvatochromic shift properties of this molecule, showed ten excited singlet states for DPCP in the UV region. This indicates minimum overlap of the electronic transition bands computationally. The increased ΔELUMO-HOMO (4.09 - 4.31eV), I and ƞ, the lower dipole moments and polarizability values as solvent polarity increased, suggests high stability of this compound in polar solvents. The excess polarizabilities obtained for its singlet excited states show that the excited state of this compound is more polar than its ground state, and that, the molecule is chemically active.
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References
Adeoye, M. D., Obi-Egbedi, N. O., & Iweibo, I. (2012). Solvent effect and photo-physical properties of 2, 3-diphenylcyclopropenone. Arabian Journal of Chemistry. doi:http://dx.doi.org/10.1016/j.arabjc.2012.06.019
Arivazhagan., M., Subhasini, V. P., & Austine, A. (2012). Vibrational spectroscopic,first-order hyper-polarizability and HOMO, LUMO studies of 4-chloro-2- (trifluoromethyl) aniline based on DFT calculations,. Spectrochim. Acta Part A, 86 :205–213.
Ashraf , A. A., Alaa, A. H., Mohsen , A., & El-Sheref, E. M. (2007). Unusual reactivity of thiosemicarbazides towards 2,3-diphenylcyclopropenone: synthesis of new pyridazinethiones and 1,2,4-triazolo[4,3-b]pyridazinethiones. . ARKIVOC (xiv), 1-11.
Bo, H., Chan, Y., & Qingwei, W. (2011). Electron-withdrawing substituted BTD-based derivatives: Electron and optical properties, charge transfer, stability study. . Journal of Theo. and Comput. Chem.10 (6), 829-838.
Borbulevych , O. Y., Clark , R. D., Romero, A., Tan , L., Antipin, M. Y., Nesterov, V. N., . . . Timofeeva, M. (2002). Experimental and theoretical study of the structure of N,N-dimethyl-4-nitroaniline derivatives as model compounds for non-linear optical organic materials. Journal of Molecular Structure, 604, 73-86.
Breslow, R., Haynie, R., & Mirra, J. (1965). Diphenylcyclopropenone. Jornal of American. Chem. Soc., 87(6): 1320-1325.
Damian , D. L., & Thompson, J. F. (2007). Treatment of extensive cutaneous metastatic melanoma with topical sensitizer. Journal of America Academy Dermatologist, 56(5), 869–871.
Deperasinska, I. M.-H. (2007). Theoretical analysis of the electronic ground and excited Franck-Condon state of 2-Alkylamino-(3, 5 or 6)- methyl-4-nitropyridine N-oxides. Acta physica polonica A. , 112: S71-S82.
Eric, L., Amy, K., & Lisa, Z. (2007). Modeling Excited of Fluorescent Compounds with UV-Vis Spectra Calculations. Jornal of Student Comp. Chem.1:, 1-6.
Foresman, J. B., & Frisch, A. (1996). Exploring Chemistry with Electronic Structure methods, Second Edn. Pittaburgh, USA.: Gausian Incorpration.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman Jr., J. R., . . . Pople, J. A. (2004). Gaussian 03, Revision C.02, Gaussian Inc. Wallingford CT: Gaussian Incorporation.
Gerlings, P., De-Proft, F., & Langeneaker, W. (2003). Conceptual density functional theory. Chemical Review, 103, 1793.
Gotwals, R., & Sendlinger, S. (2006). In Chemistry educational guide to molecular modelling. North Carolina Central University Durham, NC. Calculation of molecular properties, 4 – 12.
Grozema, F. C., Telesca, R., Jonkman, H. T., Siebbeles , L. D., & Snijders, J. G. (n.d.). Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory. Journal of Chemical Physics, 115, 10014–10021.
Iweibo, I. C.-E. (1991). Excited states electric dipole polarizabilities and moments by solvent spectral frequency shifts: aniline, phenol and naphthalene. . Spectrochim. Acta 47(6), 705-712.
Joshi, S., & Pant, D. (2012). Solvatochromic shift and estimation of dipole moment of quinine sulphate dication. World Academy of Science, Engineering and Technology, 6, 3-29.
Kosar B, A. C. (2012). Molecular structure, spectroscopic investigations, second-order nonlinear optical properties and intramolecular proton transfer of (E)- 5-(diethylamino)-2-[(4- propylphenylimino) methyl]phenol: A combined experimental and theoretical study. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 93: 1- 9.
Obi-Egbedi, N. O, Targema, M., Adeoye, M. D., & Gbangban, S. T. (2015). Calculation of Electronic Properties of Some 4-Nitroaniline Derivatives: Molecular Structure and Solvent Effects. Int. Res. . Jornal. of Pure & App. Chem. 8(3):, 165-174.
Potts, K. T., & Baum, J. S. (1974). Chemistry of cyclopropenones. Chem. Rev.,, 74(2): 189–213.
Raikar , U. S., Tangod, V. B., Mastiholi, B. M., & Sreenivasa, S. (2010). Solvent effects and photophysical studies of ADS560EI laser dye. African Journal of Pure and Applied Chemistry, 4(9), 188-197.
Ramegowda, M. (2013). Theoretical study of the absorption spectra of triamterene. . International Journal of pharmaceutical Sciences and research., 4(3): 1192-1195.
Shubing, L. (2005). Dynamic behavior of chemical reactivity indices in density functional theory: A Bohn–Oppenheimer quantum molecular dynamics study. Journal of Chemical Science, 117(5), 477–483.
Udhayakala, P., Jayanthi , A., Rajendiran , T. V., & Gunasekaran, S. (2011). Molecular structure, FT-IR and FT-Raman spectra and HOMOLUMO analysis of 2-methoxy-4-nitroaniline using ab initio HF and DFT (B3LYP/B3PW91) calculations. Archives of Appled Science Resolution, 3 (4), 424-439.
Wang , S., & Ho, T. (2000). Substituent effects on intra-molecular charge-transfer behaviour of styrylheterocycles. Journal of Photochemistry and Photobiology A (Chemistry), 119–126.
Ya-Ying, Z., Fu-Ming, T., & Eddy, Y. Z. (2008). Theoretical study of quantitative structure-activity relationships for the toxicity of dibenzo-p-dioxins. Chemosphere 73:, 86-9.