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The impact of sampling methods on spectral broadening in the gas phase and on the convergence of spectra in aqueous solution when using microsolvation, continuum solvation, and hybrid models is studied using pyrazine as a test case. For the sake of comparing classical Maxwell–Boltzmann and Wigner samplings in the gas phase, static and time-resolved X-ray absorption spectra after photoexcitation to the lowest 1B2u(ππ*) state, as well as the static UV–vis absorption spectrum, are considered. In addition, the UV–vis absorption spectrum of pyrazine in aqueous solution is also computed in order to systematically investigate its convergence with the number of explicitly included solvent shells with and without taking bulk solvation effects into account with the conductor-like screening model to represent implicit water beyond such explicit solute complexes. Concerning the static and time-resolved X-ray absorption spectra of pyrazine at the carbon K-edge as well as its UV–vis absorption spectrum in the gas phase, we find that these spectra obtained with Wigner and Maxwell–Boltzmann samplings substantially agree. For the UV–vis absorption spectrum in the aqueous solution, only the first two energetically low-lying bands converge quickly with the size of the explicitly included solvation shells, either with or without an additional continuum solvation taken into account. In stark contrast, calculations of the higher-lying excitations relying on finite microsolvated clusters without additional continuum solvation severely suffer from unphysical charge-transfer excitations into Rydberg-like orbitals at the cluster/vacuum interface. This finding indicates that computational UV–vis absorption spectra covering sufficiently high-lying states converge only if continuum solvation of the explicitly microsolvated solutes is included in the models.

The closely related second-order methods CC2 and ADC(2) usually perform very similarly for single excitations of organic molecules. However, as rationalized in this work, significant deviations between these two methods can arise if the ground state and a low-lying singly excited state arise from a strong coupling between their leading configurations. Such a configuration mixing is partially accounted for in CC2 through the ground-state singles amplitudes but is omitted in ADC(2). This can cause unusual deviations between the results obtained with these methods. In this work, we study how severe this effect can become at the example of two solvatochromic dyes: the negatively solvatochromic betaine dye N1-tBuand the positively solvatochromic bithiophene P1. These two dyes allow one to study the limits of both small and somewhat larger excitation energies and configuration mixing by tuning the S0→ S1transition energy through the polarity of the environment. Higher-level calculations at the CC3 level provide information on the accuracy of ADC(2) and CC2 in these cases. The most extreme deviation between ADC(2) and CC2 is found for N1-tBuin vacuum, where the ADC(2) result is 0.45 eV below that of CC2. In this case, the methodical error of CC2 with respect to CC3 is only 0.05 eV. With increasing excitation energy in polar solvents, the CC2–ADC(2) deviation decreases and reaches a value of only 0.15 eV. For P1, which has larger excitation energies, these effects are reversed due to the opposite solvatochromism but also smaller in magnitude: the deviation increases from 0.08 eV in vacuum to 0.16 eV in the so-called conductor limit of the continuum solvation model. Although for these two dyes larger deviations are observed for smaller excitation energies, the extent of configuration mixing does not generally correlate with only the size of excitation energy. For example, s-triazine (0.15 eV), formamide (0.19 eV), and formaldehyde (0.23 eV) also show large deviations between CC2 and ADC(2) despite their much higher excitation energies compared to those of N1-tBuand P1.

The absorption and magnetic circular dichroism (MCD) spectra of purine and of the purine nucleobases adenine and guanine have been calculated in gas phase at the Coupled Cluster Singles and Doubles (CCSD) and Resolution-of-Identity Singles and Approximate Doubles (RI-CC2) levels of theory. Exploiting a new development in the TURBOMOLE program package for computing vertical excitation energies and Faraday Bterms in an implicit solvent approximated by the conductor-like screening model (COSMO) at the CC2 level, we have investigated the solvent effects on the relative positions of the ππ* and nπ* electronic transitions in these three molecules and compared them to the corresponding vacuum results. In the case of adenine, we also included specific solvent effects with a small water cluster. The spectra obtained with the implicit model COSMO are in qualitative agreement with those obtained with explicit water molecules both with and without the inclusion of the bulk solvent effects via the continuum solvent model. This suggests that the inclusion of the electrostatic contributions of the solvent can provide a sufficiently accurate description of the absorption spectra for adenine. The results for purine, adenine, and guanine show that, after the inclusion of bulk solvation, the ππ* states shift to lower energies while at the same time nπ* states show a reversed behavior. The computed MCD spectra show the characteristic bisignate profile found experimentally in all cases, despite, for adenine, remarkable differences in the origin of the individual peaks for different computational methods. Therefore, the ability (or inability) of MCD to determine the relative stability of the Laand Lbstates is critically reassessed. According to our best estimate for adenine in aqueous solution, the Lastate is more stable than Lb.