Skip to main content
SpringerLink
Log in

An Experimental and Theoretical Test of Dielectric Friction Models Using Rotational Diffusion of 7-Diethylamino-2-H-1-Benzopyran-2-One in Non-associative Solvents

  • ORIGINAL ARTICLE
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

The rotational re-orientations times of the 7-DHB dye molecule have been examined in non-associative solvents (DMSO and Octanenitrile) by varying the temperature, by employing the Steady-State Fluorescence Depolarisation and Time-Correlated Single Photon Counting (TCSPC) techniques. Rotational re-orientations time values in DMSO are found larger by a factor of 1.136 than octanenitrile, which indicates that 7-DHB laser dye is experiencing higher friction in DMSO than octanenitrile. To determine mechanical friction Stokes Einstein’s Debye theory (SED) -with a stick, slip boundary conditions parameters are used and found an interesting super slip trend. Point dipole models as Nee-Zwanzig (NZ) and van der Zwan-Hynes (ZH) fail to explain experimental dielectric friction observed trends. Alavi-Waldeck model successfully explains the observed dielectric friction trend in non-associative solvents.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Mali KS, Dutt GB, Mukherjee T (2008) Rotational diffusion of a nonpolar and a dipolar solute in 1-butyl-3-methylimidazolium hexafluorophosphate and glycerol: interplay of size effects and specific interactions. J Chem Phys 128:054504–1-054504-9. https://doi.org/10.1063/1.2827473

    Article  CAS  PubMed  Google Scholar 

  2. Tao T (1969) Time-dependent fluorescence depolarization and Brownian rotational diffusion coefficients of macromolecules. Biopolymers. 8:609–632

    Article  CAS  Google Scholar 

  3. Einstein A (1956) Investigations in Theory of Brownian Motion. Dover, New York

  4. Kubinyi M, Grofcsik A, Pápai I, Jones WJ (2003) Rotational reorientation dynamics of nile blue a and oxazine 720 in protic solvents. Chem Phys 286:81–96. https://doi.org/10.1016/S0301-0104(02)00908-4

    Article  CAS  Google Scholar 

  5. Zhou P, Song P, Liu J, Shi Y, Han K, He G (2008) Rotational reorientation dynamics of oxazine 750 in polar solvents. J Phys Chem A 112:3646–3655. https://doi.org/10.1021/jp7120998

    Article  CAS  PubMed  Google Scholar 

  6. Raikar US, Renuka CG, Nadaf YF, Mulimani BG, Karguppikar AM (2006) Rotational diffusion and solvatochromic correlation of coumarin 6 laser dye. J Fluoresc 16:847–854. https://doi.org/10.1007/s10895-006-0126-4

    Article  CAS  PubMed  Google Scholar 

  7. Gangamallaiah V, Dutt GB (2012) Rotational diffusion of nonpolar and ionic solutes in 1-Alkyl-3- methylimidazolium bis (trifluoromethylsulfonyl) imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation? J Phys Chem B 116:12819–12825. https://doi.org/10.1021/jp307959z

    Article  CAS  PubMed  Google Scholar 

  8. Prabhu SR, Dutt GB (2014) Rotational diffusion of nonpolar and charged solutes in propylammonium nitrate-propylene glycol mixtures: does the organized structure of the ionic liquid influence solute rotation? J Phys Chem B 118:2738–2745. https://doi.org/10.1021/jp501343k

    Article  CAS  PubMed  Google Scholar 

  9. Prabhu SR, Dutt GB (2014) Rotational diffusion of nondipolar and charged solutes in alkyl-substituted imidazolium triflimides: effect of C2 methylation on solute rotation. J Phys Chem B 118:9420–9426. https://doi.org/10.1021/jp5055155

    Article  CAS  PubMed  Google Scholar 

  10. Nadaf YF, Renuka CG, Raikar US (2013) Temperature-dependent reorientation dynamics of laser dyes in alkane and alcohol solvents. Can J Phys 91:677–681

    Article  CAS  Google Scholar 

  11. Anirban Sharma, Pradip Kr. Ghorai (2018) Effect of alcohols on the structure and dynamics of [BMIM][PF6] ionic liquid: a combined molecular dynamics simulation and Voronoi tessellation investigation. J Chem Phys 148: 204514–1–204514–11. https://doi.org/10.1063/1.5008439

  12. Nadaf YF, Renuka CG (2015) Analysis of rotational diffusion of coumarin laser dyes. Can J Phys 93:3–6

    Article  CAS  Google Scholar 

  13. Dutt GB, Ghanty TK (2004) Rotational dynamics of nondipolar probes in butanols: correlation of reorientation times with solute-solvent interaction strengths. J Phys Chem A 108:6090–6095. https://doi.org/10.1021/jp048601q

    Article  CAS  Google Scholar 

  14. Hay CE, Marken F, Blanchard GJ (2010) Solvent-dependent changes in molecular reorientation dynamics: the role of solvent-solvent interactions. J Phys Chem A 114:4957–4962. https://doi.org/10.1021/jp912217r

    Article  CAS  PubMed  Google Scholar 

  15. Jin H, Baker GA, Arzhantsev S, Dong J, Maroncelli M (2007) Solvation and rotational dynamics of coumarin 153 in ionic liquids: comparisons to conventional solvents. J Phys Chem B 111:7291–7302. https://doi.org/10.1021/jp070923h

    Article  CAS  PubMed  Google Scholar 

  16. Kumar PV, Maroncelli M (2000) The non-separability of dielectric and mechanical friction in molecular systems: a simulation study. J Chem Phys 112(12):5370–5381. https://doi.org/10.1063/1.481107

    Article  CAS  Google Scholar 

  17. Prabhu SR, Dutt GB (2015) Rotational diffusion of charged and nondipolar solutes in ionic liquid-organic solvent mixtures: evidence for stronger specific solute-solvent interactions in presence of organic solvent. J Phys Chem B 119:10720–10726. https://doi.org/10.1021/acs.jpcb.5b06297

    Article  CAS  PubMed  Google Scholar 

  18. Dutt GB (2005) Molecular rotation as a tool for exploring specific solute-solvent interactions. Chem Phys Chem 6:413–418. https://doi.org/10.1002/cphc.200400337

    Article  CAS  PubMed  Google Scholar 

  19. Guo J, Han KS, Mahurin SM, Baker GA, Hillesheim PC, Dai S, Hagaman EW, Shaw RW (2012) Rotational and translational dynamics of rhodamine 6G in a pyrrolidinium ionic liquid: a combined time-resolved fluorescence anisotropy decay and NMR study. J Phys Chem B 116:7883–7890

    Article  CAS  Google Scholar 

  20. Tiwari AK, Sonu SSK (2014) Effect of hydroxyl group substituted spacer group of cationic gemini surfactants on solvation dynamics and rotational relaxation of coumarin-480 in aqueous micelles. J Phys Chem B 118:3582–3592. https://doi.org/10.1021/jp4069703

    Article  CAS  PubMed  Google Scholar 

  21. Nee TW, Zwanzig R (1970) Theory of dielectric relaxation in polar liquids. J Chem Phys 52:6353–6363. https://doi.org/10.1063/1.1672951

    Article  CAS  Google Scholar 

  22. Hu C, Zwanzig R (1974) Rotational friction coefficients for spheroids with the slipping boundary condition. J Chem Phys 60:4354–4357

    Article  CAS  Google Scholar 

  23. Madden P, Kivelson D (1982) Dielectric friction and molecular reorientation. J Phys Chem 86:4244–4256. https://doi.org/10.1021/j100218a031

    Article  CAS  Google Scholar 

  24. Van Der Zwan G, Hynes JT (1985) Time-dependent fluorescence solvent shifts, dielectric friction, and nonequilibrium solvation in polar solvents. J Phys Chem 89:4181–4188. https://doi.org/10.1021/j100266a008

    Article  Google Scholar 

  25. Ben-Amotz D, Drake JM (1988) The solute size effect in rotational diffusion experiments: a test of microscopic friction theories. J Chem Phys 89:1019–1029. https://doi.org/10.1063/1.455253

    Article  CAS  Google Scholar 

  26. Simon JD, Thompson PA (1990) Spectroscopy and rotational dynamics of oxazine 725 in alcohols: a test of dielectric friction theories. J Chem Phys 92:2891–2896. https://doi.org/10.1063/1.457936

    Article  CAS  Google Scholar 

  27. Alavi DS, Hartman RS, Waldeck DH (1991) A test of continuum models for dielectric friction. Rotational diffusion of phenoxazine dyes in dimethylsulfoxide. J Chem Phys 94:4509–4520. https://doi.org/10.1063/1.460606

    Article  CAS  Google Scholar 

  28. Goudar R, Gupta R, Kulkarni GU, Inamdar SR (2015) Rotational diffusion of a new large non polar dye molecule in alkanes. J Fluoresc 25:1671–1679. https://doi.org/10.1007/s10895-015-1654-6

    Article  CAS  PubMed  Google Scholar 

  29. Horng ML, Gardecki JA, Maroncelli M (1997) Rotational dynamics of coumarin 153: time-dependent friction, dielectric friction, and other nonhydrodynamic effects. J Phys Chem A 101:1030–1047. https://doi.org/10.1021/jp962921v

    Article  CAS  Google Scholar 

  30. Maroncelli M (1997) Continuum estimates of rotational dielectric friction and polar solvation. J Chem Phys 106:1545–1555. https://doi.org/10.1063/1.473276

    Article  CAS  Google Scholar 

  31. Dutt GB, Raman S (2001) Rotational dynamics of coumarins: an experimental test of dielectric friction theories. J Chem Phys 114:6702–6713. https://doi.org/10.1063/1.1357797

    Article  CAS  Google Scholar 

  32. Mannekutla JR, Inamdar SR, Mulimani BG, Savadatti MI (2010) Rotational diffusion of Coumarins: a dielectric friction study. J Fluoresc 20:797–808. https://doi.org/10.1007/s10895-010-0606-4

    Article  CAS  PubMed  Google Scholar 

  33. Inamdar SR, Mannekutla JR, Mulimani BG, Savadatti MI (2006) Rotational dynamics of nonpolar laser dyes. Chem Phys Lett 429:141–146. https://doi.org/10.1016/j.cplett.2006.08.020

    Article  CAS  Google Scholar 

  34. Hughes RM, Mutzenhardt P, Bartolotti L, Rodriguez AA (2008) Experimental and theoretical analysis of the reorientational dynamics of fullerene C70 in various aromatic solvents. J Phys Chem A 112:4186–4193. https://doi.org/10.1021/jp800027j

    Article  CAS  PubMed  Google Scholar 

  35. Gayathri BR, Mannekutla JR, Inamdar SR (2008) Rotational diffusion of coumarins in alcohols: a dielectric friction study. J Fluoresc 18:943–952

    Article  CAS  Google Scholar 

  36. Dutt GB, Rama Krishna G (2001) Rotational dynamics of coumarins in nonassociative solvents: point dipole versus extended charge distribution models of dielectric friction. J Chem Phys 115:4732–4740

    Article  CAS  Google Scholar 

  37. Lackowicz JR (1983) Principles of fluorescence spectroscopy. Plenum, New York

    Book  Google Scholar 

  38. Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S, Windus TL, Dupuis M, Montgomery JA (1993) General atomic and molecular electronic structure system. J Comput Chem 14:1347–1363

    Article  CAS  Google Scholar 

  39. Renuka CG, Shivashankar K, Boregowda P, Bellad SS, Muregendrappa MV, Nadaf YF (2017) An experimental and computational study of 2-(3-Oxo3H-benzo[f] chromen-1-ylmethoxy)-benzoic acid methyl Ester. J Solut Chem 46:1535–1555. https://doi.org/10.1007/s10953-017-0661-4

    Article  CAS  Google Scholar 

  40. Renuka CG, Nadaf YF, Sriprakash G, Rajendra Prasad S (2018) Solvent dependence on structure and electronic properties of 7-(Diethylamino) – 2H -1- Benzopyran −2- one (C-466) laser dye. J Fluoresc 28:839–854. https://doi.org/10.1007/s10895-018-2249-9

    Article  CAS  PubMed  Google Scholar 

  41. Edward JT (1970) Molecular volumes and the stokes-Einstein equation. J Chem Educ 47:261–270. https://doi.org/10.1021/ed047p2613/1.1680910

    Article  CAS  Google Scholar 

  42. Fleming GR (1986) Chemical applications of ultrafast spectroscopy. Oxford University Press, London

    Google Scholar 

  43. Small EW, Isenberg I (1977) Hydrodynamic properties of a rigid macromolecule: rotational and linear diffusion and fluorescence anisotropy. Biopolymers 16:1907–1928

    Article  CAS  Google Scholar 

  44. Sension RJ, Hochstrasser RM (1993) Comment on: rotational friction coefficients for ellipsoids and chemical molecules with slip boundary conditions. J Chem Phys 98:2490

    Article  CAS  Google Scholar 

  45. Gierer VA, Wirtz K (1953) Molecular theory of microreiberation. Z. Naturforschg 8A:532-

    Google Scholar 

  46. Bagchi B, Jana B (2010) Solvation dynamics in dipolar liquids. Chem Soc Rev 39:1936–1954. https://doi.org/10.1039/b902048a

    Article  CAS  PubMed  Google Scholar 

  47. Das SK, Majhi D, Sahu PK, Sarkar M (2015) Investigation of the influence of alkyl side chain length on the fluorescence response of C153 in a series of room temperature ionic liquids. RSC Adv 5:41585–41594. https://doi.org/10.1039/C4RA16864J

    Article  CAS  Google Scholar 

  48. Rosenthal SJ, Jimenez et al (1994). Solvation dynamics in methanol: Experimental and molecular dynamics simulation studies. J Mol Liq 60:25–56. https://doi.org/10.1016/0167-7322(94)00738-1

  49. Simon JD (1988) Time-resolved studies of solvation in polar media. Acc Chem Res 21:128–134. https://doi.org/10.1021/ar00147a006

    Article  CAS  Google Scholar 

  50. Yevheniia S, François-Alexandre M et al (2017) Solvation dynamics and rotation of coumarin 153 in a new ionic liquid/molecular solvent mixture model: [BMIM][TFSI]/propylenecarbonate. J Mol Liq 226:48–55. https://doi.org/10.1016/j.molliq.2016.10.00

    Article  Google Scholar 

  51. Zhang XX, Liang M, Ernsting NP, Maroncelli M (2013) Complete solvation response of coumarin 153 in ionic liquids. J Phys Chem B 117:4291–4304. https://doi.org/10.1021/jp305430a

    Article  CAS  PubMed  Google Scholar 

  52. Dutta GB, Rama Krishna G (2001) Rotational dynamics of coumarins in nonassociative solvents: point dipole versus extended charge distribution models of dielectric friction. J Chem Phys 115:4732–4741. https://doi.org/10.1063/1.1395563

    Article  CAS  Google Scholar 

  53. Dutt GB (2000) Rotational dynamics of non-dipolar probes in alkane–alkanol mixtures: microscopic friction on hydrogen bonding and non-hydrogen bonding solute molecules. J Chem Phys 113:11154–11158

    Article  CAS  Google Scholar 

  54. Alavi DS, Waldeck DH (1991) Rotational dielectric friction on a generalized charge distribution. J Chem Phys 94:6197–6202

    Google Scholar 

  55. Hartman RS, Waldeck DH (1994) Rotational diffusion of fluorenes in Dimethyl Sulfoxide. J Phys Chem 98:1386–1393

    Article  CAS  Google Scholar 

  56. Hartman RS, Waldeck DH (1991) An experimental test of dielectric friction models using the diffusion of aminoanthraquinones. J Phys Chem 95:7872–7880

    Article  CAS  Google Scholar 

  57. Kurnikova MG, Waldeck DH, Coalson RD (1996) A molecular dynamic study of dielectric friction. J Chem Phys 105:628–638

    Article  CAS  Google Scholar 

  58. Panwang Z, Jianyon L, Peng S, Heli K, Guozhing H (2009) Rotational reorientation dynamics of rhodamine 700 in different excited states. J Lumin 129:283–289

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. P.G. Department of Physics, Sri Siddeshwara Government First Grade College, Naragund, 582207, India

    Anil Kumar

  2. Department of Physics, Jnanabharathi campus, Bangalore University, Bengaluru, 560056, India

    C. G. Renuka

  3. Department of Physics and Research Center, Maharani Science College for Women, Bengaluru, 560001, India

    Y. F. Nadaf

Authors
  1. Anil Kumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. C. G. Renuka
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Y. F. Nadaf
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Y. F. Nadaf.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kumar, A., Renuka, C.G. & Nadaf, Y.F. An Experimental and Theoretical Test of Dielectric Friction Models Using Rotational Diffusion of 7-Diethylamino-2-H-1-Benzopyran-2-One in Non-associative Solvents. J Fluoresc 29, 899–909 (2019). https://doi.org/10.1007/s10895-019-02402-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-019-02402-3

Keywords

Search

Navigation