Role of Singles Amplitudes in ADC(2) and CC2 for Low-Lying Electronically Excited States.

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-tBu and 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 → S1 transition 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-tBu in 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-tBu and P1.

Computational investigation of explicit solvent effects and specific interactions of hydroxypyrene photoacids in acetone, DMSO, and water.

This work employs the correlated wavefunction-based methods ADC(2) and CC2 in combination with the implicit solvent model COSMO to calculate the UV/Vis absorption and fluorescence emission energies of particularly strong hydroxypyrene photoacids in acetone. According to the Förster cycle, the electronic transition energies are first used to compute , i.e., the pKa change upon excitation and then the excited-state pKa (labeled ) with ground-state pKa values based on COSMO-RS as additional inputs. Furthermore, for the strongest photoacid of that class, namely tris(1,1,1,3,3,3-hexafluoropropan-2-yl)-8-hydroxypyrene-1,3,6-trisulfonate, the need to go beyond implicit solvation and to account for explicit solvent effects on the electronic transition energies and the resulting ΔpKa is investigated in the solvents acetone, dimethyl sulfoxide (DMSO), and water. For this, a hybrid implicit-explicit approach is followed by comparing micro-solvated structures that are generated based on Kamlet-Taft considerations. While implicit solvent effects are mostly sufficient for the aprotic solvent acetone, one explicit solvent molecule seems relevant for DMSO due to its stronger hydrogen-bond (HB) acceptance and hence larger interaction with the photoacid OH group as a HB donor. For the protic solvent water, the situation is more complicated, involving at least one water molecule at the OH group and up to three water molecules at the O- group of the corresponding base. Finally, these results are used to rationalize the experimentally observed spectral evolution of the photoacid absorption band in acetone-water solvent mixtures.

Ultrafast transient absorption and solvation of a super-photoacid in acetoneous environments.

The phenomenon of photoacidity, i.e., an increase in acidity by several orders of magnitude upon electronic excitation, is frequently encountered in aromatic alcohols capable of transferring a proton to a suitable acceptor. A promising new class of neutral super-photoacids based on pyranine derivatives has been shown to exhibit pronounced solvatochromic effects. To disclose the underlying mechanisms contributing to excited-state proton transfer (ESPT) and the temporal characteristics of solvation and ESPT, we scrutinize the associated ultrafast dynamics of the strongest photoacid of this class, namely tris(1,1,1,3,3,3-hexafluoropropan-2-yl)8-hydroxypyrene-1,3,6-trisulfonate, in acetoneous environment, thereby finding experimental evidence for ESPT even under these adverse conditions for proton transfer. Juxtaposing results from time-correlated single-photon counting and femtosecond transient absorption measurements combined with a complete decomposition of all signal components, i.e., absorption of ground and excited states as well as stimulated emission, we disclose dynamics of solvation, rotational diffusion, and radiative relaxation processes in acetone and identify the relevant steps of ESPT along with the associated time scales.

Theoretical Study on the Photoacidity of Hydroxypyrene Derivatives in DMSO Using ADC(2) and CC2.

This work applies the thermodynamic Förster cycle to theoretically investigate the pKa*, i.e., excited-state pKa values of pyranine-derived superphotoacids developed by Jung and co-workers. The latter photoacids are strong enough to transfer a proton to the aprotic solvent dimethyl sulfoxide (DMSO). The Förster cycle provides access to pKa* via the ground-state pKa and the electronic excitation energies. We use the conductor-like screening model for real solvents (COSMO-RS) to compute the ground-state pKa and the correlated wavefunction-based methods ADC(2) and CC2 with the continuum solvation model COSMO to calculate the pKa change upon excitation. A comparison of the calculated UV/Vis absorption and fluorescence emission energies to the experimental results leads us to infer that this approach allows for a proper description of the electronic excitations. In particular, implicit solvation by means of the COSMO model appears to be sufficient for the treatment of these photoacids in DMSO. The calculations confirm the presumption that a charge redistribution from the hydroxy group to the aromatic ring and the electron-withdrawing substituents is the origin of photoacidity for these photoacids. Moreover, the calculations with the continuum solvation model predict that the pKa jump upon excitation decreases with increasing solvent polarity, as rationalized based on the Förster cycle.

Prediction of acid pKa values in the solvent acetone based on COSMO-RS.

In this contribution we extent the use of the conductor-like screening model for realistic solvation (COSMO-RS) to the prediction of pKa values in acetone, a commonly used dipolar aprotic solvent. For this, we calculated the Gibbs free energy of dissociation of 120 organic acids (nine acrylic acids, 87 benzoic acids, nine phenols, and 15 benzenesulfonamides) using COSMO-RS at the two levels BP-TZVP and BP-TZVPD-FINE and determined the parameters for a linear free energy relation for the pKa prediction by performing linear fits to experimental values. Our results suggest that the data set dissects into two groups, with the phenols being different from the other three subsets. The acrylic and benzoic acids and the sulfonamides can be treated together and yield an excellent linear correlation ( r2>0.95 ) with an RMSD of only ~0.3. The slope is found to be significantly smaller than the theoretical value ( 1/RTln10 ), only 45% of it, which is in accordance with findings in the literature. The phenols, however, while similarly well correlated in their own subset with an RMSD of 1.7-1.9, exhibit a slope larger than one. We discuss both a higher uncertainty in the reference values as well as physical origins as possible reasons.