28 December 2001 ELSEVIER (Chemical Physics Letters 390 (2001) 509-514 VA CHEMICAL PHYSICS LETTERS srw eleven comlocatleplet On the relationship between the radiative rate constant and the fluorescence intensity in organic fluorophores JA. Tuszytiski *, JM. Dixon *, Y, Engelborghs © * Deparement of Physics, University of Alberta. Ednonton, ABerta, Canada TAG 21 * Deparment of Physics, versity of Warwick, Cacentry CV TAL, UK * Laboratory of Blomolecular Dynamis, Uncorty of Lewen, Celestinonaan 200D, 3001 Lewsen, Belgium Received 26 Apri 200: in final fran 25 October 2001 Abstract In this Letter we explore the relationship between the radiative constant, k, and the lineshape of an emission spectrum for floreseeat organic molecules, in particular tryptophan, We make a number of judicious spproximations {o the expression given by Strickler and Berg in conjunction with the log-normal function for te lineshape. Our result is 1 closed form expression for A, in terms of the inverse maximum wavelength 4, which compares well with recent ‘experimental ndings for tryptophan residues in proteins, © 2001 Elsevier s jence BLY. All rights reserved 1, Introduction Siano and Metzler [1] demonstrated that the shape of the emission spectra of complex organic molecules can be adequately described by a four- parameter log-normal function. This function, for iv) > 0, can be written in a mirror symmetic form as [2] A{v) = Jyexp{ — (In2/In" p) -In? ((a—v)/(a—v%)] } uy where Joy = I(vp) is the maximal fluorescence in- tensity, va is the wavenumber of the hand maxi- mum and p is defined by “Corresponding author. Fax: +44-024-7660-2016 E-mail oddress: pisinGawarwick.ae uke (LM. Dison) (0009-26 14/015 - swe front matter © 2001 Elsevier Science B.V) PIL: $0009-2614(01}01301-X. 9 = Om = VIO = Ye. (2) This latter describes the band symmetry pa- rameter and v, and y are the wavenumber posix tions of left and right half-maximal amplitudes. The parameter @ is the function limiting point where a= in + Hallo’ ~ 1) a3) and H is the band width given by H=y (14) Decay associated spectra are constructed by ‘multiplying the intensity fraction by the intensity of the spectra for a given wavelength [3] where again the intensity is represented by the log-nor- ‘mal function in terms of the wavelength as a-WWa wee (Sai) ] exp | (as) 1) Al eights reservedS10 A, Tusapish etal Chemteal PhsiesLesers 380 (2001) 500-804 (1.6) 7) The values 4, and A have been given [4] a5 Ay = 107 /(0.830 x 10° /2q + 7071), {L8) 107/(1.1768 « 10" fg ~ 7681), (19) where Jy is in nanometers. The wavelength of maximal emission, Zn, for fluorescent probes in proteins such as tryptophan is sensitive tothe environment in which the protein is located. In fact, a relationship has been obtained between the radiative rate constant, &, and the mum wavelength [5,6] and is given by [7] LO Gig) | pear where g, and gy are the degeneracies of the lower ‘and upper state and mis the refractive index. The parameter «isthe molar absorption coefiient and Vis the wavenumber 2/7 In this Letter we will be interested primarily in expressing the radiative rate constant, de in terms of the maximum wavelength, Zp, ie, we wish (0 obtain an explicit relationship hy = hol (ies any ‘where F{ém) will be approximated by the ratio of the two integrals in Eq. (1.10). pas “ xr (Mg ® 2. Approximating (2) Eq, (1.5) will be our starting point. For the pur- pose of approximating this formula we notice that p is a number very close to unity. Therefore we will introduce an expansion parameter ¢ given by Mig = 1/2 = fhe + Way sapol Tie bes en and we will estimate one of the factors in the ex- ponent is +e e2) Focussing on one of the other factors in the ex- ponential we find +H 23) -)[k-(et)] on (-a)G-4) For the range of wavelengths contributing to the lineshape the values of w are reasonably small so thal we can once again use a power series expan sion for the logarithm so that In ta)~ at 2s) so that Therefore the special intensity function can be el: cgantly expressed by ina( 12) and in the following section we will exploit this particular form in evaluating the ensuing in- tegrals, 3, Estimating the integrals over the intensity The first step is to change the variable of inte- gration from the wavenumber ¥ to the wavelength J according to ¥ = 2x7 so that dh @.) In addition, the volume element in reciprocal (hree-dimensional) space is given byJA, Tasik ofa | Chemis Physics Letters 380 (2001) $09 S14 su 40 = 4nv°de, 62) Hence, we find that pu)ay Sv) a Substituting 7() in Eq, @.7) into Bq. 3.3) we obtain G3) 5 sen (—N(4-1) ee fe texp(="(4= Z= (2) 3.5) changes Eq. (3.4) into (4x) exp(-me)dr = 3.6) (d+s) ‘exp(—Neyar Close to the point x = ~1/ the denominator will be very large and the contribution to Z very small Te is therefore a good approximation to replace the lower fimit of both integrals in Eq, (3.6) by zero. We then expand the factor (Iffg +x) ' in the denominator as (+s) =200 and evaluate the resulting Gaussian integrals by using. dur lt) GI) [fe G8) fe omar 39) and [ee ae G.10) where denotes an Euler gamma fonction [8] 0 that PQ) = va, F(1) = 1, and £3) = 1. With these intexrals substituted into Eq. (3.6) we find {m? wana aac Ly} eu Subsequently we expand the denominator in a power series about unity so that Z is approximated by the formula (244 a} +48), G12) 13) G14) ‘The final step consists of arranging Eq. 3.12) in powers of Ja Which is then substituted into the expression for the radiative rate constant given in Eq, (1.10), We find that where the expansion coefficients have been caleu- lated and are given by a ( (316) G ot ae |r Gan (Qnay' * 2yntina) 12 G8)