International E-publication: Publish Projects, Dissertation, Theses, Books, Souvenir, Conference Proceeding with ISBN.  International E-Bulletin: Information/News regarding: Academics and Research

Change in Energy of Hydrogen Bonds upon Excitation of Coumarin 1: TDDFT/EFP1 Method

Author Affiliations

  • 1PG Department of Physics, Govt. College (Autonomous), Mandya - 571401, INDIA

Res.J.chem.sci., Volume 3, Issue (7), Pages 25-30, July,18 (2013)


Density functional theory (DFT)/ Time dependent density functional theory (TDDFT) calculations combined with the effective fragment potential (EFP) method have been carried out to study the electronic structure and the exited state properties of Coumarin 1 with three water molecules (C1-(H2O)3 complex). Ground-state geometries are optimized using DFT with B3LYP functional combined with cc-pVDZ basis set and transition energies are computed with same basis set and functional. Three intermolecular hydrogen bonds are formed in C1-(H2O)3 complex, one N⋯H–O (type A) by amino group of C1 with one water molecule and two C=O⋯H–O (type B) by carbonyl group of C1 with two water molecules. The change in hydrogen bond energy, ΔEHB of C1-(H2O)3 molecule and ΔEHB for each HB of C1-(H2O)3 molecule are calculated separately. Upon excitation of C1-(H2O)3 complex, A type HB is weakened with decrease of 4.783 kJ/mol energy, whereas B type HBs are strengthened with increase of 9.614 kJ/mol energy. In this theoretical work, it is confirmed again that, due to excitation, intermolecular hydrogen bonds between aminocoumarins and polar solvents are strengthened, not cleaved, as reported by Zhao’s, Wiley Periodicals, Inc. J. Comput. Chem., (2011).


  1. Liu Y., Ding J., Liu R., Shi D. and Sun J., Changes in energy of three types of hydrogen bonds upon excitation of aminocoumarins determined from absorption solvatochromic experiments, J. Photochem. Photobiol. A, 201, 203 (2009)
  2. Zhou P., Song P., Liu J., Han K. and He G., Experimental and theoretical study of the rotational reorientation dynamics of 7-aminocoumarin derivatives in polar solvents: hydrogen-bonding effects, Phys. Chem. Chem. Phys., 11, 9440 (2009)
  3. Liu Y., Ding J., Shi D. and Sun J., Time-dependent density functional theory study on electronically excited states of coumarin 102 chromophore in aniline solvent: reconsideration of the electronic excited-state hydrogen-bonding dynamics, J. Phys. Chem. A, 112, 6244 (2008)
  4. Miao M. and Shi Y., Reconsideration on hydrogen bond strengthening or cleavage of photoexcited coumarin 102 in aqueous solvent: a DFT/TDDFT study, J. Comput. Chem., 32, 3058 (2011)
  5. Liu Y-H. and Li P., Excited-state hydrogen bonding effect on dynamic fluorescence of coumarin 102 chromophore in solution: A time-resolved fluorescence and theoretical study, J. Lumin., 131, 2116 (2011)
  6. Pines E., Pines D., Ma Y-Z. and Fleming G.R., Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions, Chem. Phys. Chem., 5(9), 1315 (2004)
  7. Nibbering E.T.J., Fidder H. and Pines E., Ultrafast Chemistry: Using Time-resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics, Annu. Rev. Phys. Chem., 56, 337 (2005)
  8. Zhao G-J. and Han K-L., Hydrogen bonding in the electronic excited state, Acc. Chem. Res., 45, 404 (2012)
  9. Zhao G-J. and Han K-L., Ultrafast hydrogen bond strengthening of the photoexcited fluorenone in alcohols for facilitating the fluorescence quenching, J. Phys. Chem. A, 111, 9218 (2007)
  10. Zhao W., Pan L., Bian W. and Wang J., Influence of solvent polarity and hydrogen bonding on the electronic transition of coumarin 120: a TDDFT study, Chem. Phys. Chem., , 1593 (2008)
  11. Zhao G-J., Liu J-Y., Zhou L-C. and Han K-L., Site-selective photoinduced electron transfer from alcoholic solvents to the chromophore facilitated by hydrogen bonding: a new fluorescence quenching mechanism, J. Phys. Chem. B, 111, 8940 (2007)
  12. Zhao G-J. and Han K-L., Effects of hydrogen bonding on tuning photochemistry: concerted hydrogen-bond strengthening and weakening, Chem.Phys.Chem.,9, 1842 (2008)
  13. Zhao G-J. and Han K-L., Early time hydrogen-bonding dynamics of photoexcited coumarin 102 in hydrogen-donating solvents: theoretical study, J. Phys. Chem. A, 111, 2469, (2007)
  14. Zhao G-J. and Han K-L., Hydrogen Bonding and Transfer in the Excited State, John Wiley & Sons Ltd (2011)
  15. Morimoito A., Yatsuhashi T., Shimada T., Biczok L., Tryk D.A. and Inoue H., Radiationless deactivation of an intramolecular charge transfer excited state through hydrogen bonding: Effect of molecular structure and hard-soft anionic character in the excited state, J. Phys. Chem. A, 105, 10488 (2001)
  16. Biczok L., Berces T. and Linschitz H., Quenching Processes in Hydrogen-Bonded Pairs: Interactions of Excited Fluorenone with Alcohols and Phenols, J. Am. Chem. Soc., 119, 11071 (1997)
  17. Kyrychenko A. and Waluk J., Excited-state proton transfer through water bridges and structure of hydrogen-bonded complexes in 1H-pyrrolo[3,2-h]quinoline: adiabatic time-dependent density functional theory study, J. Phys. Chem. A, 110, 11958 (2006)
  18. Krystkowiak E. and Maciejewski A., Changes in energy of three types of hydrogen bonds upon excitation of aminocoumarins determined from absorption solvatochromic experiments, Phys. Chem. Chem. Phys., 13, 11317 (2011)
  19. Wang H., Wang M., Liu E., Xin M. and Yang C., DFT/TDDFT study on the excited-state hydrogen bonding dynamics of hydrogen-bonded complex formed by methyl cyanide and methanol, Comput. Theor. Chem., 964, 243, (2011)
  20. Wang H, Wang M, Xin M, Liu E, Yang C., Excited-state hydrogen bonding dynamics of methyl isocyanide in methanol solvent: A DFT/TDDFT study, Cent. Eur. J. Phys., , 792 (2011)
  21. Jones II G., Jackson W.R. and Halpern A.M., Medium effects on fluorescence quantum yields and lifetimes for coumarin laser dyes, Chem. Phys. Lett., 72, 391 (1980)
  22. Lopez A.T., Lopez A.F., Tapia M.J. and Arbeloa I.L., Hydrogen-bonding effect on the photophysical properties of 7-aminocoumarin derivatives, J. Phys. Chem., 97, 4704 (1993)
  23. Lopez A.T., Lopez A.F., Tapia M.J. and Arbeloa I.L., Binary solvent effects on the absorption and emission of 7-aminocoumarins, J. Lumin., 59, 369 (1994)
  24. Matsubayashi K. and Kubo Y., Control of Photophysical Properties and Photoreactions of Aromatic Imides by Use of Intermolecular Hydrogen Bonding, J. Org. Chem., 73, 4915, (2008)
  25. Samant V., Singh A.K., Ramakrishna G., Ghosh H.N., Ghanty T.K. and Palit D.K., Ultrafast Intermolecular Hydrogen Bond Dynamics in the Excited State of Fluorenone , J. Phys.Chem. A, 109, 8693 (2005)
  26. Munoz M.A., Galan M., Gomez L., Carmona C., Guardado P. and Balon M., The pyrrole ring as hydrogen-bonding donor base: an experimental and theoretical study of the interactions of N-methylpyrrole with alcohols, J.Chem. Phys., 290, 69 (2003)
  27. Carmona C., Balon M., Galan M., Guardado P. and Munoz M.A., Dynamic Study of Excited State Hydrogen-bonded Complexes of Harmane in Cyclohexane–Toluene Mixtures, Photochem. Photobiol., 76, 239 (2002)
  28. Carmona C., Balon M., Galan M., Guardado P. and Munoz M.A., Kinetic Study of Hydrogen Bonded Exciplex Formation of N-methyl Harmane, J. Phys. Chem. A, 105, 10334 (2001)
  29. Day P.N., Jensen J.H., Gordon M.S., Webb S.P., Stevens W.J., Krauss M., Garmer D., Basch H. and Cohen D., An effective fragment method for modeling solvent effects in quantum mechanical calculations, J. Chem. Phys. 105, 1968 (1996)
  30. Gordon M.S., Freitag M.A., Bandyopadhyay P., Jensen J.H., Kairys V. and Stevens W.J., The Effective Fragment Potential Method: A QM-Based MM Approach to Modeling Environmental Effects in Chemistry, J. Phys. Chem. A,105, 293 (2001)
  31. Adamovic I., Freitag M.A. and Gordon M.S., Density functional theory based effective fragment potential method, J. Chem. Phys., 118, 6725 (2003)
  32. Yoo S., Zahariev F., Sok S. and Gordon M.S., Solvent effects on optical properties of molecules: A combined time-dependent density functional theory/effective fragment potential approach, J. Chem. Phys., 129, 144112 (2008)
  33. Si D. and Li H., Analytic energy gradient in combined time-dependent density functional theory and polarizable force field calculation, J. Chem. Phys., 133, 144112 (2010)
  34. Minizawa N., De Silva N., Zahariev F. and Gordon M.S., Implementation of the analytic energy gradient for the combined time-dependent density functional theory/effective fragment potential method: Application to excited-state molecular dynamics simulations, J. Chem. Phys., 134, 54111 (2011)
  35. Nicoud J.F. and Twieg R.J., Non-linear optical properties of Organic molecules Crystals, Academic, Orlo, FL (2002) ch. II-3.
  36. Gustavsson T., Cassara T.L., Gulbinas V., Gurzadyan G., Mialocq J-C., Pommeret S., Sorgius M. and Van Der Meulen P., Femtosecond Spectroscopic Study of Relaxation Processes of Three Amino-Substituted Coumarin Dyes in Methanol and Dimethyl Sulfoxide, J. Phys. Chem. A, 102, 4229 (1998)
  37. Pal H., Nad S. and Kumbhakar M., Photophysical properties of coumarin-120: Unusual behavior in nonpolar solvents, J. Chem. Phys., 119, 442 (2003)
  38. Moog R.S., Kim D.D., Oberle J.J. and Ostrowski S.G., Solvent Effects on Electronic Transitions of Highly Dipolar Dyes: A Comparison of Three Approaches, J. Phys. Chem. A, 108, 9294 (2004)
  39. Neugebauer J., Jacob C.R.,Wesolowski T.A. and Baerends E.J., An Explicit Quantum Chemical Method for Modeling Large Solvation Shells Applied to Aminocoumarin C151, J. Phys. Chem., 109, 7805 (2005)
  40. Sulpizi M., Rhrig U.F., Hutter J. and Rothlisberger U., Optical properties of molecules in solution via hybrid TDDFT/MM simulations, Int. J. Quantum. Chem., 101, 671 (2004)
  41. Nguyen K.A., Day P.N. and Pachter R., Effects of solvation on one- and two-photon spectra of coumarin derivatives: A time-dependent density functional theory study, J. Chem. Phys., 126, 094303 (2007)
  42. Improta R., Barone V. and Santoro F., Ab Initio Calculations of Absorption Spectra of Large Molecules in Solution: Coumarin C153, Angew. Chem., 119, 409 (2007)
  43. Sulpizi M., Carloni P., Hutter J. and Rothlisberger U., A hybrid TDDFT/MM investigation of the optical properties of aminocoumarins in water and acetonitrile solution, Phys. Chem. Chem. Phys., , 4798 (2003)
  44. Kina D., Arora P., Nakayama A., Noro T., Gordon M.S. and Taketsugu T., Ab initio QM/MM excited-state molecular dynamics study of coumarin 151 in water solution, Int. J. Quantum. Chem., 109, 2308 (2009)
  45. Schmidt M.W., Baldridge K.K., Boatz J.A., Elbert S.T., Gordon M.S., Jensen J.H., Koseki S., Matsunaga N., Nguyen K.A., Su S.J., Windus T.L., Dupuis M. and Montgomery J.A., General atomic and molecular electronic structure system, J. Comput. Chem. 14, 1347-1363 (1993)
  46. Gordon M.S. and Schmidt M.W., Advances in electronic structure theory, GAMESS a decade laterChapter 41, pp 1167-1189, in Theory Applications of Computational Chemistry, the first forty yearsDykstra C.E., Frenking G., Kim K.S., Scuseria G.E., Editors (Elsevier, Amsterdam, 2005)