Open AccessDonor properties of the three carbonyl groups of chlorophyll a: ab initio calculations and 13C magnetic resonance studies.
Author(s) -
Lester L. Shipman,
Thomas R. Janson,
G. Joseph Ray,
Joseph Katz
Publication year - 1975
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.72.8.2873
Subject(s) - chemistry , ab initio , dimer , polarizability , binding energy , resonance (particle physics) , computational chemistry , ab initio quantum chemistry methods , dipole , photochemistry , crystallography , molecule , atomic physics , organic chemistry , physics
The relative donor properties of the three carbonyl groups of chlorophyll a have been studied theoretically by a series of ab initio molecular fragment, floating spherical Gaussian orbital, self-consistent field calculations on ethyl chlorophyllide a and experimentally through a 13C magnetic resonance study on chlorophyll a. The approximate ground state electronic wavefunction of ethyl chlorophyllide a was perturbed by monopole and dipole point charges whose signs, magnitudes, and positions were chosen to mimic the coulombic interactions associated with carbonyl coordination to Mg. Because the polarizability of the ring V keto carbonyl binding site is substantially greater than that for the ester carbonyl binding sites, the ring V keto binding site binds with smallest binding energy for weak perturbations and with largest binding energy for strong perturbations. A comparison of 13C magnetic resonance chemical shifts in chlorophyll a monomer and dimer provides new experimental evidence that the donor-acceptor interactions that bind the chlorophyll dimer together involve a substantial participation by the ring V keto carbonyl and minimal participation by the two ester carbonyl groups, and thus are in agreement with conclusions derived from the ab initio calculations.