Signatures in Vibrational and Vibronic Spectra of Benzene Molecular Clusters.

Abstract

The photoabsorption and infrared spectra (IR) of molecular systems are heavily influenced by aggregation. In the electronic spectra, the vibronic coupling effect is of utmost importance. Although treating both effects simultaneously can be challenging, it is often the only way to explain the experimental spectrum of molecular clusters. In this work, we study IR spectra and the vibronic coupling effect in the electronic photoabsorption spectra in molecular systems composed of benzene (monomer, dimers, and crystal). Photoabsorption spectra were generated using the direct vibronic coupling method at the density functional theory (DFT) level. We also simulated the spectra with the Liouville-Lanczos approach by calculating the electronic transitions along the main inducing modes for two forbidden transitions (¹A_1g → ¹B_2u and ¹A_1g → ¹B_1u). DFT was also applied to simulate IR spectra. For the monomer, vibronic coupling was crucial to induce the first and second forbidden transitions. On the other hand, molecular aggregation was sufficient to induce the first and second forbidden transitions in almost all dimers. However, when the vibronic coupling is evaluated for the clusters, the band in the energy range of the ¹A_1g → ¹B_1u transition is affected both by the aggregation itself and the inducing modes. Moreover, some inducing modes drastically change the allowed ¹A_1g → ¹E_1u transition, depending on the dimer under study due to symmetry breaking. In terms of IR spectra, clear signatures are present. For instance, the intensities of the C-H stretching modes decrease as aggregation increases. This work shows that aggregation impacts the band shapes differently in relation to the benzene aggregate structure and the excitation under analysis.