Aromatic Excimers: <i>Ab Initio</i> and TD-DFT Study

Excited dimers (excimers) formed by aromatic molecules are important in biological systems as well as in chemical sensing. The structure of many biological systems is governed by excimer formation. Since theoretical studies of such systems provide important information about mutual arrangement of aromatic molecules in structural biology, we carried out extensive calculations on the benzene excimer using EOM-CCSD, RI-CC2, CASPT2, and TD-DFT approaches. For the benzene excimer, we evaluate the reliability of the TD-DFT method based on the B3LYP, PBE, PBE0, and ωPBEh functionals. We extended the calculations to naphthalene, anthracene, and pyrene excimers. We find that nearly parallel stacked forms are the minimum energy structure. On the basis of the benzene to pyrene excimers, we might roughly estimate the equilibrium layer-to-layer distance for bilayer-long arenes in the first singlet excited state, which is predicted to be bound

Halogen−π Interactions between Benzene and X₂/CX₄ (X = Cl, Br): Assessment of Various Density Functionals with Respect to CCSD(T)

Various types of interactions between halogen (X) and π moiety (X−π interaction) including halogen bonding play important roles in forming the structures of biological, supramolecular, and nanomaterial systems containing halogens and aromatic rings. Furthermore, halogen molecules such as X₂ and CX₄ (X = Cl/Br) can be intercalated in graphite and bilayer graphene for doping and graphene functionalization/modification. Due to the X−π interactions, though recently highly studied, their structures are still hardly predictable. Here, using the coupled-cluster with single, double, and noniterative triple excitations (CCSD­(T)), the Møller–Plesset second-order perturbation theory (MP2), and various flavors of density functional theory (DFT) methods, we study complexes of benzene (Bz) with halogen-containing molecules X₂ and CX₄ (X = Cl/Br) and analyze various components of the interaction energy using symmetry adapted perturbation theory (SAPT). As for the lowest energy conformers (S1), X₂–Bz is found to have the T-shaped structure where the electropositive X atom-end of X₂ is pointing to the electronegative midpoint of CC bond of the Bz ring, and CX₄–Bz has the stacked structure. In addition to this CX₄–Bz (S1), other low energy conformers of X₂–Bz (S2/S3) and CX₄–Bz (S2) are stabilized primarily by the dispersion interaction, whereas the electrostatic interaction is substantial. Most of the density functionals show noticeable deviations from the CCSD­(T) complete basis set (CBS) limit binding energies, especially in the case of strongly halogen-bonded conformers of X₂–Bz (S1), whereas the deviations are relatively small for CX₄–Bz where the dispersion is more important. The halogen bond shows highly anisotropic electron density around halogen atoms and the DFT results are very sensitive to basis set. The unsatisfactory performance of many density functionals could be mainly due to less accurate exchange. This is evidenced from the good performance by the dispersion corrected hybrid and double hybrid functionals. B2GP-PLYP-D3 and PBE0-TS­(Tkatchenko-Scheffler)/D3 are well suited to describe the X−π interactions adequately, close to the CCSD­(T)/CBS binding energies (within ∼1 kJ/mol). This understanding would be useful to study diverse X−π interaction driven structures such as halogen containing compounds intercalated between 2-dimensional layers

Comparison of cationic, anionic and neutral hydrogen bonded dimers

Short Strong Hydrogen Bonds (SSHBs) play an important role in many fields of physics, chemistry and biology. Since it is known that SSHBs exist in many biological systems, the role of hydrogen bonding motifs has been particularly interesting in enzyme catalysis, bio-metabolism, protein folding and proton transport phenomena. To explore the characteristic features of neutral, anionic and cationic hydrogen bonds, we have carried out theoretical studies of diverse homogeneous and heterogeneous hydrogen bonded dimers including water, peroxides, alcohols, ethers, aldehydes, ketones, carboxylic acids, anhydrides, and nitriles. Geometry optimization and harmonic frequency calculations are performed at the levels of Density Functional Theory (DFT) and Moller-Plesset second order perturbation (MP2) theory. First principles Car-Parrinello molecular dynamics (CPMD) simulations are performed to obtain IR spectra derived from velocity-and dipole-autocorrelation functions. We find that the hydrogen bond energy is roughly inversely proportional to the fourth power of the r(O/N-H) distance. Namely, the polarization of the proton accepting O/N atom by the proton-donating H atom reflects most of the binding energy in these diverse cation/anion/neutral hydrogen bonds. The present study gives deeper insight into the nature of hydrogen-bonded dimers including SSHBs.close151

Aromatic Excimers: Ab Initio and TD-DFT Study

Excited dimers (excimers) formed by aromatic molecules are important in biological systems as well as in chemical sensing. The structure of many biological systems is governed by excimer formation. Since theoretical studies of such systems provide important information about mutual arrangement of aromatic molecules in structural biology, we carried out extensive calculations on the benzene excimer using EOM-CCSD, RI-CC2, CASPT2, and TD-DFT approaches. For the benzene excimer, we evaluate the reliability of the TD-DFT method based on the B3LYP, PBE, PBE0, and ??PBEh functionals. We extended the calculations to naphthalene, anthracene, and pyrene excimers. We find that nearly parallel stacked forms are the minimum energy structure. On the basis of the benzene to pyrene excimers, we might roughly estimate the equilibrium layer-to-layer distance for bilayer-long arenes in the first singlet excited state, which is predicted to be bound.close7