Species generally exhibit one-state aromaticity either in the lowest singlet state (S0 ) or the lowest triplet state (T1 ) according to the Hückel's and Baird's rules. Hence, it is rare for species exhibit two-state aromaticity in both the S0 and T1 states (termed as adaptive aromaticity), let alone adaptive σ aromaticity. Here, we report adaptive σ aromaticity in unsaturated rhenacyclopropene rings via density functional theory (DFT) calculations. Various aromaticity indices including NICS, ACID, EDDB together with isodesmic reactions support the adaptive σ aromaticity in these rhenacyclopropene rings. As the T1 state of these species is formed by the ππ* excitation, the σ-aromaticity of these three-membered rings in the S0 state could hold in the T1 state. In addition, the aromaticity effect of the fused rings is also examined. Our findings expand the family of adaptive σ aromaticity, enriching the metallaaromatic chemistry.

Growth pattern and electronic and magnetic properties of Agn Cr (n = 1-16) clusters have been investigated via density functional theory (DFT) combined with CALYPSO structure search method. The optimized geometry shows that the growth of the global minimum structures of Agn Cr clusters have obvious rule. when n > 12, silver atoms grow around an icosahedron which is almost unchanged in each structure. Analyses of electronic properties indicate that the doped Cr atom can only enhance the stability of larger silver clusters. Optical absorption and photoelectron spectra of Agn Cr isomers have been predicted and can be used for their structural identification. The icosahedral Ag12 Cr cluster with large energy level gap can be seen as a superatom. The adsorption capacity of Cr atom in Agn Cr cluster to CO is much higher than that of free Cr atom. The intensity of IR and Ramam spectra can be dramatically enhanced when CO is absorbed on Agn Cr cluster that Cr atom is encapsulated by Ag atoms. Moreover, the red shift of IR and Raman spectra of CO adsorbed on these clusters is also very small compared to free CO. Magnetism calculations show that the magnetic moment of Agn Cr clusters decreases linearly from n = 6 to 12 and increases linearly from n = 12 to 16. The total magnetic moment of Agn Cr cluster is mainly localized on the Cr atom. The change of magnetic moment of Cr atom is related to the charge transfer between Cr and Ag atoms.

UV-VIS photoinduced events of tz A and tz G embedded into DNA and RNA are described by combining the Extended Multi-State Second-Order Perturbation Theory (XMS-CASPT2) and electrostatic embedding molecular mechanics methods (QM/MM). Our results point out that the S1 1 (ππ* La ) state is the bright state in both environments. After the photoexcitation to the S1 1 (ππ* La ) state, the electronic population evolves barrierless towards its minimum, from where the excess of energy can be dissipated by fluorescence. As the minimum energy crossing point structure between the ground and first bright states lies in a high-energy region, the direct internal conversion to the ground state is an unviable mechanism. Other spectroscopic properties (for instance, absorption and Stokes shifts) and comparisons with photochemical properties of canonical nucleobases are also provided.

Diketopyrrolopyrrole (DPP) systems have promising applications in different organic electronic devices. In this work, we investigated the effect of 20 different substituent groups on the optoelectronic properties of DPP-based derivatives as the donor ( D )-material in an organic photovoltaic (OPV) device. For this purpose, we employed Hammett's theory (HT), which quantifies the electron-donating or -withdrawing properties of a given substituent group. Machine learning (ML)-based σm , σp , σm0 , σp0 , σp+ , σp- , σI , and σR Hammett's constants previously determined were used. Mono- (DPP-X1 ) and di-functionalized (DPP-X2 ) DPPs, where X is a substituent group, were investigated using density functional theory (DFT), time-dependent DFT (TDDFT), and ab initio methods. Several properties were computed using CAM-B3LYP and the second-order algebraic diagrammatic construction, ADC(2), an ab initio wave function method, including the adiabatic ionization potential ( IPA ), the electron affinity ( EAA ), the HOMO-LUMO gaps ( Eg ), and the maximum absorption wavelengths ( λmax ), the first excited state transition 1 S0 → 1 S1 energies ( ∆E ) (the optical gap), and exciton binding energies. From the optoelectronic properties and employing typical acceptor systems, the power conversion efficiency ( PCE ), open-circuit voltage ( VOC ), and fill factor ( FF ) were predicted for a DPP-based OPV device. These photovoltaic properties were also correlated with the machine learning (ML)-based Hammett's constants. Overall, good correlations between all properties and the different types of σ constants were obtained, except for the σI constants, which are related to inductive effects. This scenario suggests that resonance is the main factor controlling electron donation and withdrawal effects. We found that substituent groups with large σ values can produce higher photovoltaic efficiencies. It was also found that electron-withdrawing groups (EWGs) reduced Eg and ∆E considerably compared to the unsubstituted DPP-H. Moreover, for every decrease (increase) in the values of a given optoelectronic property of DPP-X1 systems, a more significant decrease (increase) in the same values was observed for the DPP-X2 , thus showing that the addition of the second substituent results in a more extensive influence on all electronic properties. For the exciton binding energies, an unsupervised machine learning algorithm identified groups of substituents characterized by average values (centroids) of Hammett's constants that can drive the search for new DDP-derived materials. Our work presents a promising approach by applying HT on molecular engineering DPP-based molecules and other conjugated molecules for applications on organic optoelectronic devices.

To reduce the climate impact of thermal engines such as heat pumps or refrigeration machines, refrigerants with a low global warming potential need to be paired with fitting lubricants. As the contamination of those liquid components influences the efficiency and lifetime of these machines, knowledge about their solubility behavior is of great interest. Molecular simulations offer mighty tools to investigate these solubilities while giving structural insight into the systems. Here the solubility behavior of CO2 , R-32, R-1233zd(E), and R-1234yf in PEB8, PEC4, and PEC8 is compared through the solvation free energy ∆GSolv obtained by molecular dynamics simulations. To derive ∆GSolv at low computational cost, an iterative method is used to find an optimal number and distribution of intermediate states. The resulting distributions are investigated with regard to different parameters of the employed softcore-potential. ∆GSolv values for the different refrigerant-lubricant pairings at different temperatures are provided, followed by a structural analysis.