Aiguo Zhong

Origin of anomeric effect: A density functional steric analysis

The anomeric effect (the tendency of heteroatomic substituents adjacent to a heteroatom within the cyclohexane ring to prefer the axial orientation instead of the sterically less hindered equatorial position) is traditionally explained through either the dipole moment repulsion or the hyperconjugation effect. In this work, by employing our recent work in density functional steric analysis, we provide a novel two-component explanation, which is consistent with the common belief in chemistry that the effect has a stereoelectronic origin. With α-D-glucopyranose as the prototype, we systematically explore its conformational space and generate 32 isomers, leading to a total of 80 axial-equatorial conformation pairs. The energy difference analysis of these pairs shows that while statistically speaking the tendency is valid, the anomeric effect is not always true and can be violated. Three energy components, exchange-correlation, classical electrostatic, and density functional steric, are found to be directly proportional to the total energy difference between axial and equatorial isomers. We also found that the total dipole moment change, not the hyperconjugation effect, is a reasonable indicator of the total energy difference. However, all these correlations alone are not strong enough to provide a compellingly convincing explanation for the general validity of the effect. With the help of strong correlations between energy components, an explanation with two energy components, steric and electrostatic, was proposed in this work. We show that the axial-equatorial energy difference in general, with the anomeric effect as a special case, is dictated by two factors of the stereoelectronic origin, steric hindrance and classical electrostatic interactions, synchronously working together. Another explanation in terms of exchange-correlation and electrostatic interactions has also been obtained in this work.

Towards understanding performance differences between approximate density functionals for spin states of iron complexes

Density functional theory has been widely used to investigate the structural and electronic properties of heme-containing proteins such as cytochrome P450. Nevertheless, recent studies have shown that approximate exchange-correlation energy density functionals can incorrectly predict the stability order of spin states in, for instance, iron-containing pyridine and imidazole systems. This raises questions about the validity of earlier theoretical studies. In this work, we systematically investigate a few typical inorganic and organic iron-containing complexes and try to understand the performance difference of various density functionals. Two oxidation states of iron, Fe(II) and Fe(III), with different spin states and both adiabatic and vertical structures are considered. A different description of the outmost molecular orbital is found to play the crucial role. Local density and generalized gradient based functionals bias the lower spin state and produce a more localized frontier orbital that is higher in energy than the hybrid functionals. Energy component analysis has been performed, together with comparison of numerous structural and electronic properties. Implications of the present work to the theoretical study of heme-containing biological molecules and other spin-related systems are discussed.

VALIDITY AND INTERPRETATION OF HUND'S MULTIPLICITY RULE FOR MOLECULES: A DENSITY FUNCTIONAL STUDY

Validity and interpretation of Hunds multiplicity rule for one molecular system, boron hydride, is investigated from the density functional framework in the present work. Performance of a number of approximate exchange-correlaton energy denstiy functionals from LDA, GGA and hybrid models have been examined. It has been shown that all approximate functionals are able to predict the correct energy order, both adiabatically and vertically, for different spin states of the molecule, reproducing that a higher spin state from the same electronic configuration possesses a lower total energy. It is only the hybrid functionals, however, that render the picture derived for the exact density functionl theory of excited states and multiplets, that is, the validity of Hunds rule can be interpreted by the sole contribution from the outmost orbital (i.e. HOMO) of the spin states. Systematic discrepancy between the total and HOMO energy differences have been observed for both LDA and GGA forms, indicating that they are not as good in simulating the same-spin electron correlation effect as the Hartree–Fock method. We also show that it is the same as what we have found from the Hartree–Fock theory, and justification via either the nuclear-electron attraction or the exchange energy alone is not adequate to interpret the validity of the rule.

Molecular acidity: An accurate description with information-theoretic approach in density functional reactivity theory

Molecular acidity is one of the important physiochemical properties of a molecular system, yet its accurate calculation and prediction are still an unresolved problem in the literature. In this work, we propose to make use of the quantities from the information‐theoretic (IT) approach in density functional reactivity theory and provide an accurate description of molecular acidity from a completely new perspective. To illustrate our point, five different categories of acidic series, singly and doubly substituted benzoic acids, singly substituted benzenesulfinic acids, benzeneseleninic acids, phenols, and alkyl carboxylic acids, have been thoroughly examined. We show that using IT quantities such as Shannon entropy, Fisher information, Ghosh–Berkowitz–Parr entropy, information gain, Onicescu information energy, and relative Rényi entropy, one is able to simultaneously predict experimental pKa values of these different categories of compounds. Because of the universality of the quantities employed in this work, which are all density dependent, our approach should be general and be applicable to other systems as well.

UNDERSTANDING THE ROLE OF WATER IN PROMOTING E-ISOMER PRODUCTION AND PHOTOCHROMISM OF SOLID SCHIFF BASE: A DFT AND TD-DFT STUDY

The formation mechanism and photochromic property of a novel solid state Schiff base compound (E-isomer, C21H18I2N3O2) derived from 4-aminoantipyrine and 3,5-diiodosalicylaldehyde is investigated in this work using density functional theory at the B3LYP/6-31l++G** level with and without solvent water presence. Our computational results show that the conversion in the gas phase is unlikely to occur and the solvent water is involved in the reaction to decrease the barrier height. We considered one to three water molecule participations in the water-catalyzed mechanism to produce the E-isomer. Time-dependent density functional theory (B3LYP/6-311+G*) is employed to examine the photochromic property of the molecule. A large Stokes shift between absorption and emission has been attributed to the intramolecular H-transfer (O–H⋯N to O⋯H–N) following photoexcitation of the enol species, suggesting that the keto form of the photoproduct structure plays the key role, in agreement with the experimental finding of stereoselectivity. Conceptual DFT reactivity indices are employed to rationalize the findings from the present study.