Understanding the decomposition reaction mechanism of chrysanthemic acid: a computational study
© Elroby et al 2011
Received: 2 June 2011
Accepted: 30 October 2011
Published: 30 October 2011
Chrysanthemic acid (CHA) is a major product from the photodecomposition of pyrethrin which is an important class of pesticide compounds.
In the following paper, Hybrid density functional theory (DFT) calculations of the potential energy surface (PES) for three possible channels decomposition of chrysanthemic acid (cis-trans isomerization, rearrangement and fragmentation) have been carried at the B3LYP/6-311+G** level of theory. DFT was employed to optimize the geometry parameters of the reactants, transition states, intermediates and products based on detailed potential energy surfaces (PES).
Our results suggest that all three pathways of CHA are endothermic. DFT calculations revealed that the activation barriers for cis-trans isomerization are low, leading to a thermodynamically favorable process than other two pathways. We also investigated the solvent effect on the PES using the polarizable continuum model (PCM). In addition, time-dependent density functional theory (TDDFT) calculations showed that these reactions occur in the ground state rather than in an excited state.
The rearrangement process seems to be more favorable than the decomposition of CHA to carbene formation. The solvent effect calculations indicated no changes in the shape of the PES with three continua (water, ethanol and cyclohexane), although the solvents tend to stabilize all of the species.
The main objective of this project was to carry out a theoretical study to determine the reaction mechanism of the decomposition of chrysanthemic acid. This investigation may improve our knowledge about the potential energy surface (PES) of these important compounds. We explored the potential energy surfaces of the ground state and the lowest singlet and triplet excited states and the interplay between them. DFT calculations have been used successfully in calculating transition structures  and the reaction parameters of various reactions, such as pericyclic rearrangements, cycloadditions  and bimolecular SN2 reactions . In the present work, we use the density functional (DFT) approach to undertake a theoretical investigation of the mechanism of photochemical decomposition of CHA. More specifically, we calculate structures and relative energies of reactant, products, intermediate and transition states involved in all the three suggested pathways (cis-trans isomerization, rearrangement, fragmentation). For a more complete study we also carried out the effect of solvent on the PES using the polarizable continuum model (PCM).
All calculations were performed with the Gaussian03W  program, running on a Pentium IV personal computer. We used restricted and unrestricted B3LYP gradient corrected exchange-correlation functional [23, 24] in combination with the 6-311+G** basis set [25–27]. In our computational investigation, we determined the location of the minima and transition structures of the singlet state surfaces. For equilibrium geometries and transition states, the nature of the critical points was confirmed by an analytic frequency computation. All the transition states have imaginary frequencies. We carried out IRC calculations to confirm that the transition stats connect to right minima. Zero-point vibrational energy corrections (ZPVE) were estimated at the same theory level at which optimization was carried out and Etotal was calculated as Eopt (optimization energy at equilibrium geometry) + ZPVE. Basis set superposition error (BSSE) corrections  were used to obtain more reasonable total energies in fragmentation reaction (pathway 3). Subsequently, the polarizable continuum model (PCM)  was applied considering water, ethanol, and cyclohexane as solvents (ε = 78.3553, 24.852, and 2.0165, respectively). Atomic charges were derived by natural  population analyses.
Results and discussion
Cis-trans isomerization pathway
Calculated Energies of the stationary points of rearrangement of CHA (P1-P4).
Relative energies kcal/mol
Dipole moment D.B
P 2-Triplet (inter-1)
Calculated low-energy singlet excitation energies, wavelengths, and oscillator strengths (f) for CHA (P1) using TD-B3LYP/6-311G** level.
Oscillator strength (f)
Excitation energy (eV)
HOMO-1 - > LUMO
HOMO - > LUMO
HOMO-1 - > LUMO
HOMO - > LUMO
HOMO-1 - > LUMO
The solvent does not affect the ordering stability of the potential energy surface species. However, the solvents increase the stability of all of the reaction species with increasing dielectric constants.
Potential energy surface (PES) for three channels of decomposition of CHA (P1) were studied in the gas phase at the B3LYP/6-311+G** level of theory. The solvent effect on PES was also analyzed theoretically. Based on our results and analyses, we conclude the following.
1 - The calculations rationalize and verify all experimental facts. The B3LYP/6-311+G**level of theory provides a reasonable way to investigate the decomposition channels of chrysanthemic acid.
2 - Cis-trans isomerization pathway is energetically favorable than the fragmentation and rearrangement pathways.
3 - The solvent effect does not affect the shape of the potential energy surfaces. In other words, the solvent effect on the reaction is small and tends to stabilize all of the isomers.
This Project was funded by the Deanship of Scientific Research (DSR) King Abdulaziz University, Jeddah, under grant no. MS 11/4. The authors, therefore, acknowledge with thanks DSR support for Scientific Research.
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