Calculations of Electronic Excitation Energies and Excess Electric Dipole Moments of Solvated p‑Nitroaniline with the EOM-CCSD-PCM Method

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 122; no. 29; pp. 6062 - 6070
• Main Authors: Lu, Shih-I, Gao, Li-Ting
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.07.2018
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.8b02321

We present computational evidence utilizing vertical electronic excitation energies and the corresponding excess dipole moments of solvated p-nitroaniline (pNA). The properties of interest are calculated by employing the equation of motion coupled cluster together with single and double excitations (EOM-CCSD). Solvent effects are included through the polarizable continuum model (PCM) with the state-specific (SS) formalism and the perturbation theory energy and density (PTED) approach. We examine the ground state equilibrium geometry of pNA in different environments to yield the symmetry of the stable conformer of solvated pNA is C s but is also C 2v . By employing the calculated vertical excitation energies overestimate experiment, our calculations confirm the consistency of the calculated excess dipole moments with comparable documented results. Lastly, specific to this study, dissimilar environmental models, such as the linear response (LR), and variants of the corrected linear response (cLR and cLR0) formalisms in the context of the EOM-CCSD-PCM-PTED, are assessed against those from the SS formalism.