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Donor Properties Ofthe Three Carbonyl Groups of Chlorophyll A

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Donor Properties Ofthe Three Carbonyl Groups of Chlorophyll A Proc. Nat. Acad. Sci. USA Vol. 72, No. 8, pp. 2873-2876, August 1975 Chemistry Donor properties of the three carbonyl groups of chlorophyll a: ab initio calculations and 13C magnetic resonance studies (chlorophyll self-aggregation/donor-acceptor interactions/point charge perturbations) LESTER L. SHIPMAN*, THOMAS R. JANSON*, G. JOSEPH RAYt, AND JOSEPH J. KATZ* * Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439; and t Standard Oil Company of Indiana, Naperville, Illinois 60540 Contributed by Joseph J. Katz, June 2, 1975 ABSTRACT The relative donor properties of the three In the theoretical part of the present study we have calcu- carbonyl groups of chlorophyll a have been studied theoreti- lated the coulombic binding energies of the three carbonyl cally by a series of ab initio molecular fragment, floating spherical Gaussian orbital, self-consistent field calculations functions of Chl a (ring V keto carbonyl at position 9, meth- on ethyl chlorophyllide a and experimentally through a '3C yl ester or carbomethoxy carbonyl at position 10a, and ethyl magnetic resonance study on chlorophyll a. The approximate ester or propionic carbonyl at position 7c) to gain an under- ground state electronic wavefunction of ethyl chlorophyllide standing of the relative donor abilities of the three carbonyl a was perturbed by monopole and dipole point charges groups. The potential energy component of the free energy whose signs, magnitudes, and positions were chosen to of monopole and dipole binding was computed through a se- mimic the coulombic interactions associated with carbonyl coordination to Mg. Because the polarizability of the ring V ries of twelve ab initio calculations in which first a mono- keto carbonyl binding site is substantially greater than that pole and then a dipole was brought up in turn to each of the for the ester carbonyl binding sites, the ring V keto binding three carbonyl groups along their C=O axes (Fig. 2) and the site binds with smallest binding energy for weak perturba- binding energy was calculated before and after polarization tions and with largest binding energy for strong perturba- of the electron distribution. tions. A comparison of '3C magnetic resonance chemical In the experimental part, we have compared 13C chemical shifts in chlorophyll a monomer and dimer provides new ex- perimental evidence that the donor-acceptor interactions shifts of the carbonyl carbon atoms and of carbon atoms in that bind the chlorophyll dimer together involve a substan- the vicinity of the potential donor functions in Chl a mono- tial participation by the ring V keto carbonyl and minimal mer and dimer by a titration procedure introduced by Closs participation by the two ester carbonyl groups, and thus are et al. (11). in agreement with conclusions derived from the ab initio cal- culations. Nuclear geometry of ethyl chlorophyllide a The primary events (1) in photosynthesis are generally be- The nuclear geometry for the non-hydrogen atoms used in lieved to occur within a photosynthetic unit (2-4) in which a this study was taken from the x-ray crystallographic study of large number of chlorophyll molecules act cooperatively. In Strouse (18) with the exception of the terminal carbon atoms the photosynthetic unit light energy is absorbed by antenna of the vinyl group and two ethyl groups (Fig. 1). The termi- chlorophyll and converted into electronic excitation energy; nal C-C bonds of these groups appeared too short in the this excitation energy is then transferred very efficiently (via x-ray study because of large thermal motions perpendicular excitons) to the photoreactive center (5) where charge sepa- to the terminal C-C bonds. We lengthened these bonds to ration occurs in a few special chlorophyll molecules (6). 1.39 A for the vinyl group and 1.53 A for each of the ethyl Chlorophyll a (Chl a) oligomers have been proposed (7) as groups. Because the hydrogen positions are not well-resolved realistic models for antenna chlorophyll. Infrared (8-10) and in the x-ray crystallographic studies of molecules of this size, proton magnetic resonance studies (11-13) indicate that Chl the hydrogen positions were idealized (D. Spangler, R. a dimers in nonpolar solvents are probably formed through McKinney, G. M. Maggiora, L. L. Shipman, and R. E. Chris- the coordination of the magnesium of the acceptor Chl a to be molecule to the ring V keto carbonyl oxygen of the donor toffersen, published). molecule. 13C magnetic resonance studies (14, 15) have pro- vided direct evidence that the ring V keto carbonyl of the The ab initio molecular fragment FSGO SCF approach Chl a macrocycle participates in coordination to Mg, but the The molecular quantum mechanical approach used in this extent, if any, to which the other two ester carbonyl groups study was the ab initio molecular fragment FSGO SCF ap- participate could not be deduced prior to the present study. proach (17). The ground state wavefunction is a single Slater Recently, an ab initio self-consistent field (SCF) calcula- determinant constructed from doubly occupied molecular tion (16) by the molecular fragment floating spherical orbitals which are linear combinations of floating spherical Gaussian orbital (FSGO) SCF procedure (17) on ethyl chlo- Gaussian orbitals (FSGO). The positions of the FSGO within rophyllide a (Fig. 1) has been successfully carried out. Ethyl the molecular fragments and the FSGO orbital radii were chlorophyllide a differs from Chl a only by the replacement fixed in previous studies (16-18). The linear coefficients for of the phytyl group of Chl a by an ethyl group, but is other- the basis orbitals in each of the molecular orbitals were de- wise structurally identical to Chl a. This ab initio calculation termined by the usual SCF procedure (20, 21). The ap- provided, for the first time, an approximate but complete proach is ab initio in the sense that all integrals are evalu- (i.e., both sigma and pi electrons) ground state electronic ated and none are approximated by empirical data. It has structure of the ethyl chlorophyllide a molecule. been pointed out (22) that the term "ab initio" is sometimes Abbreviations: Chi, chlorophyll; SCF, self-consistent field; FSGO, understood to imply greater accuracy than the calculations floating spherical Gaussian orbital; CPU, central processor unit. actually possess. It is, therefore, especially important to dis- 2873 Downloaded by guest on October 2, 2021 2874 Chemistry: Shipman et al. Proc. Nat. Acad. Sci. USA 72 (1975) C_ -__ _ _ 2_.06 +2 -2 / 0.39 A DIPOLE PERTURBATION _____ ~~~2.06 ~ +2 /C MONOPOLE PERTURBATION FIG. 2. Point charge magnitudes (in atomic units) and posi- tions for the dipole and monopole perturbations of a carbonyl group used in the ab initio calculations. -0.16 +0.40 P-2 ties as hydrogen bond energies, equilibrium bond lengths P- p-3 -0.49 and bond angles, rotational barriers, molecular orbital or- phytyl = In the present study we are in- -0.48 dering, and dipole moments. P-3a terested in the energy difference between the perturbed +0.04 and unperturbed system, not in the total energies them- ethyl = CH2CH3 selves, and we rely upon the assumption that our approxi- FIG. 1. Structure and partial numbering system for chlorophyll mate wavefunction for ethyl chlorophyllide a will respond a (phytyl) and ethyl chlorophyllide a (ethyl). A full numbering energetically to the coulombic perturbations in much the system is given in ref. 23. The signed numbers on the structure are same way as the exact wavefunction would respond. Fur- the 13C incremental chemical shifts [A(ppm) = 'monomer- dimer] ther, at the present level of development of large computers for the indicated carbon atoms which were recorded for Chl a en- and ab initio techniques, the molecular fragment procedure riched to 15% 13C by biosynthesis (25). Spectral data were collect- used here is a state-of-the-art technique for application to ed on a Varian CFT-20 spectrometer in pulse Fourier transform the size of ethyl chlorophyllide a. mode (3500 pulses, 1 sec recycle time). molecules Computational aspects cuss the size and quality of the basis set used in our calcula- tions. A total of 275 FSGO contracted to 239 basis functions All computations were carried out on the IBM 370/195 com- were used to describe the distribution of the 340 electrons of puter at Argonne National Laboratory. Calculations without ethyl chlorophyllide a. At 1.4 basis functions per electron polarization (i.e., without SCF iteration to convergence pair, this basis must be described as a small basis set. The under the influence of the perturbation) required 7 min of molecular fragment basis set in its present formulation (17) central processor unit (CPU)-time while calculations of the and without split inner shells (i.e., with one, not two, FSGO monopole and dipole binding energies with polarization to describe each inner shell electron pair) typically gives a (i.e., with SCF iteration to convergence) required an average total energy of approximately 85% of the energy that would of 58 and 35 min of CPU-time each, respectively. Each cal- be obtained at the Hartree-Fock limit (i.e., the lowest energy culation required 610K bytes (-153K words) of core memo- obtainable with a complete basis set and using a single Slater ry. By way of comparison, the calculation of the unper- determinant wavefunction). On a chemical scale, the differ- turbed wavefunction (16) required 2.8 hr of CPU-time, and ence between our computed total energy and the exact total this time included the one-time calculation of the two-elec- energy is large. We compute the total energy of ethyl chlo- tron integrals. The point charges, which are treated exactly rophyllide a to be -1.9 X 103 atomic units (Hartrees), and as if they were nuclei, enter into only the one-electron nu- from this we estimate the Hartree-Fock limit to be -1.9 X clear-electron interaction integrals and the nuclear-nuclear 103/0.85 = -2.2 X 103 atomic units.
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