Dominant Carbons in trans- and cis-Resveratrol Isomerization.

A comprehensive analysis for isomerization of geometric isomers in the case of resveratrol (R) has been presented. As an important red wine molecule, only one geometric isomer of resveratrol, i.e., trans-R rather than cis-R, is primarily associated with health benefit. In the present study, density function theory (DFT) provides accurate descriptions of isomerization of resveratrol. The nearly planar trans-R forms a relatively rigid and less flexible conjugate network, but the nonplanar cis-R favors a more flexible structure with steric through space interaction. The calculated carbon nuclear magnetic resonance (NMR) chemical shift indicates that all carbons are different in the isomers; it further reveals that four carbon sites, i.e., C(6) , C(8) ═C(9) , and C(11) , have a significant response to the geometric isomerization. Here C(6) is related to the steric effect in cis-R, whereas C(11) may indicate the isomerization proton transfer on C(9) linking with the resorcinol ring. The excess orbital energy spectrum (EOES) confirms the NMR "bridge of interest" carbons and reveals that five valence orbitals of 34a, 35a, 46a, 55a, and 60a respond to the isomerization most significantly. The highest occupied molecular orbital (HOMO), 60a, of the isomer pair is further studied using dual space analysis (DSA) for its orbital momentum distributions, which exhibit p-electron dominance for trans-R but hybridized sp-electron dominance for cis-R. Finally, energy decomposition analysis (EDA) highlights that trans-R is preferred over cis-R by -4.35 kcal·mol-1 , due to small electrostatic energy enhancement of the attractive orbital energy with respect to the Pauli repulsive energy.