Intermolecular interaction energies with AROFRAG-A systematic approach for fragmentation of aromatic molecules.

Intermolecular interactions with polycyclic aromatic hydrocarbons (PAHs) represent an important area of physisorption studies. These investigations are often hampered by a size of interacting PAHs, which makes the calculation prohibitively expensive. Therefore, methods designed to deal with large molecules could be helpful to reduce the computational costs of such studies.

AROFRAG─A Systematic Approach for Fragmentation of Aromatic Molecules.

We present a new systematic fragmentation scheme of polycyclic aromatic hydrocarbons (PAHs), including fullerenes and nanotubes, based on an idea to treat a sextet ring as a single unbreakable unit so that the basic unit of aromaticity remains preserved upon fragmentation. In the approach, denoted as AROFRAG (from aromatic fragmentation), a set of predefined elementary subsystems, such as naphthalene and biphenyl in the first model and larger PAHs in the second and third models, is generated with appropriate weights with the aim of reproducing the structure of the original molecule. The energies of the molecules are approximated as weighted sums of the energies of these subsystems.

Association Complexes of Calix[6]arenes with Amino Acids Explained by Energy-Partitioning Methods.

Intermolecular complexes with calixarenes are intriguing because of multiple possibilities of noncovalent binding for both polar and nonpolar molecules, including docking in the calixarene cavity. In this contribution calix[6]arenes interacting with amino acids are studied with an additional aim to show that tools such as symmetry-adapted perturbation theory (SAPT), functional-group SAPT (F-SAPT), and systematic molecular fragmentation (SMF) methods may provide explanations for different numbers of noncovalent bonds and of their varying strength for various calixarene conformers and guest molecules. The partitioning of the interaction energy provides an easy way to identify hydrogen bonds, including those with unconventional hydrogen acceptors, as well as other noncovalent bonds, and to find repulsive destabilizing interactions between functional groups.

Description of Chiral Complexes within Functional-Group Symmetry-Adapted Perturbation Theory-The Case of (S/R)-Carvone with Derivatives of (-)-Menthol.

Symmetry-adapted perturbation theory (SAPT) and functional-group SAPT (F-SAPT) are applied to examine differences in interaction energies of diastereoisomeric complexes of two chiral molecules of natural origin: (/)-carvone with (-)-menthol. The study is extended by including derivatives of menthol with its hydroxy group exchanged by another functional group, thus examining the substituent effect of the interaction and the interaction differences between diastereoisomers. The partitioning of the interaction energy into functional-group components allows one to explain this phenomenon by the mutual cancellation of attractive and repulsive interactions between functional groups.

Influence of the second layer on geometry and spectral properties of doped two-dimensional hexagonal boron nitride.

Influence of the additional layer of hexagonal boron nitride (h-BN) on structure, energetics, and electronic spectra of a layer doped with magnesium, silicon, phosphorus, aluminum, or carbon atoms has been examined by theoretical methods. The h-BN layers are modeled as BN clusters of over thirty atoms with the defect in the center. The calculations show that atom positions undergo some modifications in the presence of the second layer, which in several cases lead to significant changes in electronic spectra, like (i) modifications of the character of some states from local excitation to a partial charge transfer; (ii) redshift of the majority of lowest excitations; (iii) absence or appearance of new states in comparison with the monolayers.

The Molpro quantum chemistry package.

Molpro is a general purpose quantum chemistry software package with a long development history. It was originally focused on accurate wavefunction calculations for small molecules but now has many additional distinctive capabilities that include, inter alia, local correlation approximations combined with explicit correlation, highly efficient implementations of single-reference correlation methods, robust and efficient multireference methods for large molecules, projection embedding, and anharmonic vibrational spectra. In addition to conventional input-file specification of calculations, Molpro calculations can now be specified and analyzed via a new graphical user interface and through a Python framework.

On the applicability of functional-group symmetry-adapted perturbation theory and other partitioning models for chiral recognition - the case of popular drug molecules interacting with chiral phases.

The applicability of symmetry-adapted perturbation theory (SAPT) and functional-group SAPT (F-SAPT) to study chiral recognition is investigated on an example of three popular chiral drug molecules: ibuprofen, norepinephrine, and baclofen, interacting with phenethylamine or proline - two molecules that are often used as chiral phases in chromatography. The comparison of the F-SAPT with the interacting quantum atoms (IQA) approach is also provided. Accurate estimation of energetic differences of the non-covalent intermolecular complexes composed of two chiral molecules is a necessary prerequisite for the possibility of a prediction of the chiral recognition.

Interactions of benzene, naphthalene, and azulene with alkali-metal and alkaline-earth-metal atoms for ultracold studies.

We consider collisional properties of polyatomic aromatic hydrocarbon molecules immersed into ultracold atomic gases and investigate intermolecular interactions of exemplary benzene, naphthalene, and azulene with alkali-metal (Li, Na, K, Rb, and Cs) and alkaline-earth-metal (Mg, Ca, Sr, and Ba) atoms. We apply the state-of-the-art ab initio techniques to compute the potential energy surfaces (PESs). We use the coupled cluster method restricted to single, double, and noniterative triple excitations to reproduce the correlation energy and the small-core energy-consistent pseudopotentials to model the scalar relativistic effects in heavier metal atoms.

Dimerization Behavior of Methyl Chlorophyllide a as the Model of Chlorophyll a in the Presence of Water Molecules-Theoretical Study.

A dimerization of methyl chlorophyllide a molecules and a role of water in stabilization and properties of methyl chlorophyllide a dimers were studied by means of symmetry-adapted perturbation theory (SAPT), functional-group SAPT (F-SAPT), density-functional theory (DFT), and time-dependent DFT approaches. The quantification of various types of interactions, such as π-π stacking, coordinative, and hydrogen bonding by applying the F-SAPT energy decomposition scheme shows the major role of the magnesium atom and the pheophytin macrocycle in the stability of the complex. The examination of interaction energy components with respect to a mutual orientation of monomers and in the presence or absence of water molecules reveals that the dispersion energy is the main binding factor of the interaction, while water molecules tend to weaken the attraction between methyl chlorophyllide a species.

Substituent effects in the so-called cationπ interaction of benzene and its boron-nitrogen doped analogues: overlooked role of σ-skeleton.

Despite massive efforts to pinpoint the substituent effects in the so-called cationπ systems, no consensus has been yet reached on how substituents exercise their effects in the interaction of the aromatic molecule with the metal ion. The π-polarization (the Hunter model) and the direct local effect (the Wheeler-Houk model) are two lines of thought applied to this problem, but the justification of both approaches is based on insufficiently proven assumptions and approximations. In order to shed more light on this issue we propose a new approach which enables us to gauge directly the energetic trends resulting from the interaction of the ring with the cation.

Interaction of Non-polarizable Cations with Azaborine Isomers and Their Mono-Substituted Derivatives: Position, Induction, and Non-Classical Effects Matter.

Progress in BN/CC isosterism has opened an overwhelming urge to find prospective applications of this class of materials. Herein, the interaction of three BN isosteres of benzene, i. e.

Chiral recognition by fullerenes: CHFClBr enantiomers in the C cage.

Density-functional theory and symmetry-adapted perturbation theory calculations on complexes of the enantiomers of CHFClBr with the most stable isomer of C-3 fullerene show that despite the guests being too large for the host cage, they are nevertheless stabilized by electrostatic interactions. The complexation leads to considerable strain on the cage and the guests accompanied by compression of the bonds of the guest molecule, resulting in considerable complexation-induced changes in the infrared (IR), vibrational circular dichroism (VCD), nuclear magnetic resonance (NMR), and UV-vis spectra. The effect of chiral recognition is pronounced only for the F signal in the NMR spectra and in a sign reversal of the rotational strength of the ν stretching vibration of S-CHFClBr@C-3 in the VCD spectrum as compared to that of the free guest, making the sign of this band for the C complexes with the S- and R-guest enantiomers the same.

Interaction of Boron-Nitrogen Doped Benzene Isomers with Water.

The interaction of 1,2-dihydro-1,2-, 1,3-dihydro-1,3- and 1,4-dihydro-1,4-azaborine isomers with one and two water molecules has been studied using a variety of supermolecular (Møller-Plesset = MP, and coupled cluster = CC) as well as perturbational (symmetry-adapted perturbation theory = SAPT) electron-correlation methods in the complete basis-set limit. It has been found that the water molecule binds to azaborine isomers through O-H···π, π-H···O, and dihydrogen bonding linkages. The SAPT interaction energy decomposition shows that these complexes are mostly stabilized by dispersion followed closely by induction contributions.

A hierarchy of local coupled cluster singles and doubles response methods for ionization potentials.

We present a hierarchy of local coupled cluster (CC) linear response (LR) methods to calculate ionization potentials (IPs), i.e., excited states with one electron annihilated relative to a ground state reference.

Interplay between tetrel and triel bonds in RC6H4CN⋯MF3CN⋯BX3 complexes: A combined symmetry-adapted perturbation theory, Møller-Plesset, and quantum theory of atoms-in-molecules study.

Intermolecular ternary complexes composed of: (1) the centrally placed trifluoroacetonitrile or its higher analogs with central carbon exchanged by silicon or germanium (M = C, Si, Ge), (2) the benzonitrile molecule or its para derivatives on one side, and (3) the boron trifluoride of trichloride molecule (X = F, Cl) on the opposite side as well as the corresponding intermolecular tetrel- and triel-bonded binary complexes, were investigated by symmetry-adapted perturbation theory (SAPT) and the supermolecular Møller-Plesset method (MP2) at the complete basis set limit for optimized geometries. A character of interactions was studied by quantum theory of atoms-in-molecules (QTAIM). A comparison of interaction energies and QTAIM bond descriptors for dimers and trimers reveals that tetrel and triel bonds increase in their strength if present together in the trimer.

Structure and Energetics of Complexes of B12N12 with Hydrogen Halides-SAPT(DFT) and MP2 Study.

Molecular complexes of a fullerene analogue B12N12 with hydrogen halides (HCl, HBr, and HI) were studied with symmetry-adapted perturbation theory with density-functional theory applied for a description of monomers (SAPT(DFT)), Møller-Plesset theory to the second order (MP2), and its spin-component-scaled variant (SCS-MP2) in a limit of a complete basis set. For each halide five symmetry-distinct minimum structures of the complex have been found on the potential energy hypersurface, with interaction energies ranging from -6 to -18 kJ/mol. The natural bond orbital and the atom-in-molecules analysis of noncovalent bonds resulted in a division of these configurations into three categories: hydrogen-bonded, halogen-bonded, and those of a mixed type, involving simultaneously a hydrogen bonding and a π-hole bonding between halogen and boron atoms.

Intermolecular symmetry-adapted perturbation theory study of large organic complexes.

Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J.

Theoretical studies of potential energy surface and bound states of the strongly bound He(1S)-BeO (1Σ+) complex.

We perform electronic structure calculations of the potential energy surface of the He···BeO((1)Σ(+)) complex. We use several different methods to characterize this unusual interaction. We apply coupled cluster singles, doubles, and noniterative triples [CCSD(T)] and the multireference configuration interaction [MRCI] levels of theory.

Carbon Nanotube Container: Complexes of C50H10 with Small Molecules.

The stability of complexes of a recently synthetized (Scott et al. J. Am.

How Many Ligands Can Be Bound by Magnesium-Porphyrin? A Symmetry-Adapted Perturbation Theory Study.

The stability of complexes of magnesium-porphyrin with one or two identical ligands from the set water, pyridine, imidazole, acetate, acetonitrile, dimethyl sulfoxide (DMSO), ethyl acetate, or acetylacetone was examined using symmetry-adapted perturbation theory (SAPT) for minimum geometries obtained by density-functional theory (DFT). The nonadditive contributions to the interaction energy of the porphyrin ring with two ligands were also included and found to be very small in almost all cases. The stability of the complexes under standard conditions is predicted on the basis of the free Gibbs energy.

Small Molecules in C60 and C70: Which Complexes Could Be Stabilized?

The recent syntheses of complexes involving some small molecules in opened fullerenes and those of hydrogen molecule(s) in C60 and C70 are accompanied in the literature by numerous computations for endohedral fullerene complexes which cope with the problem of the stability of these complexes. In this contribution, stabilization energies of endohedral complexes of C60 and C70 with H2, N2, CO, HCN, H2O, H2S, NH3, CH4, CO2, C2H2, H2CO, and CH3OH guests have been estimated using symmetry-adapted perturbation theory, which, contrary to the standard DFT and some other approaches, correctly describes the dispersion contribution of the host-guest interactions. On the basis of these calculations, the endohedral complexes with all these guests were found stable in the larger fullerene, while the C60 cage was found too small to host the latter four molecules.

Interaction between LiH molecule and Li atom from state-of-the-art electronic structure calculations.

State-of-the-art ab initio techniques have been applied to compute the potential energy surface for the lithium atom interacting with the lithium hydride molecule in the Born-Oppenheimer approximation. The interaction potential was obtained using a combination of the explicitly correlated unrestricted coupled-cluster method with single, double, and noniterative triple excitations [UCCSD(T)-F12] for the core-core and core-valence correlation and full configuration interaction for the valence-valence correlation. The potential energy surface has a global minimum 8743 cm(-1) deep if the Li-H bond length is held fixed at the monomer equilibrium distance or 8825 cm(-1) deep if it is allowed to vary.

Local CC2 response method for triplet states based on Laplace transform: excitation energies and first-order properties.

A new multistate local CC2 response method for calculating excitation energies and first-order properties of excited triplet states in extended molecular systems is presented. The Laplace transform technique is employed to partition the left/right local CC2 eigenvalue problems as well as the linear equations determining the Lagrange multipliers needed for the properties. The doubles part in the equations can then be inverted on-the-fly and only effective equations for the singles part must be solved iteratively.

On the accuracy of DFT-SAPT, MP2, SCS-MP2, MP2C, and DFT+Disp methods for the interaction energies of endohedral complexes of the C(60) fullerene with a rare gas atom.

Selected points on the potential energy surface for the complexes Rg@C(60) (Rg = He, Ne, Ar, Kr) are calculated with various theoretical methods, like symmetry-adapted perturbation theory with monomers described by density functional theory (DFT-SAPT), supermolecular Møller-Plesset theory truncated on the second order (MP2), spin-component-scaled MP2 (SCS-MP2), supermolecular density functional theory with empirical dispersion correction (DFT+Disp), and the recently developed MP2C method that improves the MP2 method for long-range electron correlation effects. A stabilization of the endohedral complex is predicted by all methods, but the depth of the potential energy well is overestimated by the DFT+Disp and MP2 approaches. On the other hand, the MP2C model agrees well with DFT-SAPT, which serves as the reference.

XCC2--a new coupled cluster model for the second-order polarization propagator.

A new coupled cluster model of the polarization propagator, denoted as XCC2, is presented. The XCC2 approach employs time-independent coupled cluster theory of polarization propagators of Moszynski et al. [Collect.