Application of Time-Dependent Density Functional and Natural Bond Orbital Theories to the UV–vis Absorption Spectra of Some Phenolic Compounds

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-09, Vol.119 (35), p.9352-9362
• Main Authors: Markovic, Svetlana, Tosovic, Jelena
• Format: Article
• Language: English
• Subjects: Absorption spectra; Bonding; Clusters; Electron density; Electronics; Orbitals; Phenols; Spectra
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.5b05129

The UV–vis properties of 22 natural phenolic compounds, comprising anthraquinones, neoflavonoids, and flavonoids were systematically examined. The time-dependent density functional theory (TDDFT) approach in combination with the B3LYP, B3LYP-D2, B3P86, and M06-2X functionals was used to simulate the UV–vis spectra of the investigated compounds. It was shown that all methods exhibit very good (B3LYP slightly better) performance in reproducing the examined UV–vis spectra. However, the shapes of the Kohn–Sham molecular orbitals (MOs) involved in electronic transitions were misleading in constructing the MO correlation diagrams. To provide better understanding of redistribution of electron density upon excitation, the natural bond orbital (NBO) analysis was applied. Bearing in mind the spatial and energetic separations, as well as the character of the π bonding, lone pair, and π* antibonding natural localized molecular orbitals (NLMOs), the “NLMO clusters” were constructed. NLMO cluster should be understood as a part of a molecule characterized with distinguished electron density. It was shown that all absorption bands including all electronic transitions need to be inspected to fully understand the UV–vis spectrum of a certain compound, and, thus, to learn more about its UV–vis light absorption. Our investigation showed that the TDDFT and NBO theories are complementary, as the results from the two approaches can be combined to interpret the UV–vis spectra. Agreement between the predictions of the TDDFT approach and those based on the NLMO clusters is excellent in the case of major electronic transitions and long wavelengths. It should be emphasized that the approach for investigation of UV–vis light absorption based on the NLMO clusters is applied for the first time.