Towards the generation of potential energy surfaces of weakly bound medium-sized molecular systems: the case of benzonitrile-He complex.

Currently, the explicitly correlated coupled cluster method is used routinely to generate the multi-dimensional potential energy surfaces (mD-PESs) of van der Waals complexes of small molecular systems relevant for atmospheric, astrophysical and industrial applications. Although very accurate, this method is computationally prohibitive for medium and large molecules containing clusters. For instance, the recent detections of complex organic molecules (COMs) in the interstellar medium, such as benzonitrile, revealed the need to establish an accurate enough electronic structure approach to map the mD-PESs of these species interacting with the surrounding gases. As a benchmark, we have treated the case of the polar molecule benzonitrile interacting with helium, where we use post-Hartree-Fock and symmetry-adapted perturbation theory (SAPT) techniques. Accordingly, we show that MP2 and distinguishable-cluster approximation (DCSD) cannot be used for this purpose, whereas accurate enough PESs may be obtained using the corresponding explicitly correlated versions (MP2-F12 or DCSD-F12) with a reduction in computational costs. Alternatively, computations revealed that SAPT(DFT) is as performant as CCSD(T)-F12/aug-cc-pVTZ, making it the method of choice for mapping the mD-PESs of COMs containing clusters. Therefore, we have used this approach to generate the 3D-PES of the benzonitrile-He complex along the intermonomer Jacobi coordinates. As an application, we have incorporated the analytic form of this PES into quantum dynamical computations to determine the cross sections of the rotational (de-)excitation of benzonitrile colliding with helium at a collision energy of 10 cm-1.

Solvent-induced polymorphism in dipodal N-donor ligands containing a biphenyl core.

Polymorph screenings for two related dipodal N-donor ligands containing a biphenyl core, namely 4,4'-bis(pyridin-4-ylmethyl)-1,1'-biphenyl (1) and 4,4'-bis(1H-imidazol-1-ylmethyl)-1,1'-biphenyl (2) were performed, and the new phases were isolated and their crystal structures analysed. Profiling included methods such as PXRD and thermal analysis. Hirshfeld surface analyses, as well as crystal lattice energy calculations provided deeper insight in the interplay of the intermolecular forces and the stability of the isolated phases. Furthermore, our studies revealed the presence of solvent-induced polymorphism, whereby the metastable phase is dominant upon crystallisation from THF (1a) and EtOH (2c). Upon heating, these phases transform into a more stable form, whereby the transformations were followed by PXRD studies (1, 2).

Electronic Structure and Spectroscopy of the AuO+ Cation.

The electronic structure and spectroscopy of the 29 lowest electronic states of the AuO+ cation were studied using ab initio multiconfigurational methods. These states correlate to the Au+(1S) + O(3P) and Au+(3D) + O(3P) dissociation limits. Their potentials were calculated along the Au-O internuclear distance. There are 23 of these electronic states with potential wells deep enough to allow for long lifetimes of the AuO+ cation in the corresponding states. These bound electronic states were characterized spectroscopically by solving the radial Schrödinger equation for the nuclear motion, to deduce full sets of spectroscopic parameters. The effects of the spin-orbit coupling on the lowest electronic states have been studied by determining the potentials and spectroscopic constants of the seven lowest spin-orbit Ω components. We also carried out precise calculations to determine the adiabatic ionization energy of the AuO molecule, where several corrections of the electronic energies obtained with the standard coupled cluster approach were taken into account. Our results will facilitate the correct assignment of the IR, vis, and UV spectra of the AuO+ cation and the photoelectron spectrum of the neutral AuO diatomic.

Resolving the π-assisted U-N σf-bond formation using quantum information theory.

We model the potential energy profiles of the UO2 (NCO)Cl2- → NUOCl2- + CO2 reaction pathway [Y. Gong, V. Vallet, M. del Carmen Michelini, D. Rios and J. K. Gibson, J. Phys. Chem. A, 2014, 118, 325-330] using different pair coupled-cluster doubles (pCCD) methods. Specifically, we focus on pCCD and pCCD-tailored coupled cluster models in predicting relative energies for the various intermediates and transition states along the reaction coordinate. Furthermore, we augment our study on energetics with an orbital-pair correlation analysis of the complete reaction pathway that features two distinct paths. Our analysis of orbital correlations sheds new light on the formation and breaking of respective bonds between the uranium, oxygen, and nitrogen atoms along the reaction coordinates where the "yl" bond is broken and a nitrido compound formed. Specifically, the strengthening of the U-N σf-bond is assisted by a π-type interaction that is delocalized over the C-N-U backbone of the UO2 (NCO)Cl2- complex.

Structure, energetics, and spectroscopy of the chromophores of HHe+n, H2He+n, and He+n clusters and their deuterated isotopologues.

The linear molecular ions H2He+, HHe+2, and He+3 are the central units (chromophores) of certain He-solvated complexes of the H2He+n, HHe+n, and He+n families, respectively. These are complexes which do exist, according to mass-spectrometry studies, up to very high n values. Apparently, for some of the H2He+n and He+n complexes, the linear symmetric tetratomic H2He+2 and the diatomic He+2 cations, respectively, may also be the central units. In this study, definitive structures, relative energies, zero-point vibrational energies, and (an)harmonic vibrational fundamentals, and, in some cases, overtones and combination bands, are established mostly for the triatomic chromophores. The study is also extended to the deuterated isotopologues D2He+, DHe+2, and D2He+2. To facilitate and improve the electronic-structure computations performed, new atom-centered, fixed-exponent, Gaussian-type basis sets called MAX, with X = T(3), Q(4), P(5), and H(6), are designed for the H and He atoms. The focal-point-analysis (FPA) technique is employed to determine definitive relative energies with tight uncertainties for reactions involving the molecular ions. The FPA results determined include the 0 K proton and deuteron affinities of the 4He atom, 14 875(9) cm-1 [177.95(11) kJ mol-1] and 15 229(8) cm-1 [182.18(10) kJ mol-1], respectively, the dissociation energies of the He+2 → He+ + He, HHe+2 → HHe+ + He, and He+3 → He+2 + He reactions, 19 099(13) cm-1 [228.48(16) kJ mol-1], 3948(7) cm-1 [47.23(8) kJ mol-1], and 1401(12) cm-1 [16.76(14) kJ mol-1], respectively, the dissociation energy of the DHe+2 → DHe+ + He reaction, 4033(6) cm-1 [48.25(7) kJ mol-1], the isomerization energy between the two linear isomers of the [H, He, He]+ system, 3828(40) cm-1 [45.79(48) kJ mol-1], and the dissociation energies of the H2He+ → H+2 + He and the H2He+2 → H2He+ + He reactions, 1789(4) cm-1 [21.40(5) kJ mol-1] and 435(6) cm-1 [5.20(7) kJ mol-1], respectively. The FPA estimates of the first dissociation energy of D2He+ and D2He+2 are 1986(4) cm-1 [23.76(5) kJ mol-1] and 474(5) cm-1 [5.67(6) kJ mol-1], respectively. Determining the vibrational fundamentals of the triatomic chromophores with second-order vibrational perturbation theory (VPT2) and vibrational configuration interaction (VCI) techniques, both built around the Eckart-Watson Hamiltonian, proved unusually challenging. For the species studied, VPT2 has difficulties yielding dependable results, in some cases even for the fundamentals of the H-containing molecular cations, while carefully executed VCI computations yield considerably improved spectroscopic results. In a few cases unusually large anharmonic corrections to the fundamentals, on the order of 15% of the harmonic value, have been observed.

Buchwald-Hartwig Amination of Aryl Halides with Heterocyclic Amines in the Synthesis of Highly Fluorescent Benzodifuran-Based Star-Shaped Organic Semiconductors.

The study of palladium-catalyzed amination of bromobenzene with aromatic and heterocyclic amines, widely used in the synthesis of organic semiconductors, was performed. The best conditions for the coupling of aryl bromides with carbazole, diphenylamine, phenoxazine, phenothiazine, 9,9-dimethyl-9,10-dihydroacridine, and their derivatives have been developed. Based on the results, nine new star-shaped organic semiconductors, exhibiting up to 100% fluorescent quantum yield in the 400-550 nm range, have been synthesized in good yields. The TDDFT calculations of the absorption spectra revealed a good correlation with experimental results and slight solvatochromic effects with a change in the polarity of the solvent.

Photochemical Properties and Stability of BODIPY Dyes.

The present study is devoted to the combined experimental and theoretical description of the photophysical properties and photodegradation of the new boron-dipyrromethene (BODIPY) derivatives obtained recently for biomedical applications, such as bacteria photoinactivation (Piskorz et al., Dyes and Pigments 2020, 178, 108322). Absorption and emission spectra for a wide group of solvents of different properties for the analyzed BODIPY derivatives were investigated in order to verify their suitability for photopharmacological applications. Additionally, the photostability of the analyzed systems were thoroughly determined. The exposition to the UV light was found first to cause the decrease in the most intensive absorption band and the appearance of the hypsochromically shifted band of similar intensity. On the basis of the chromatographic and computational study, this effect was assigned to the detachment of the iodine atoms from the BODIPY core. After longer exposition to UV light, photodegradation occurred, leading to the disappearance of the intensive absorption bands and the emergence of small intensity signals in the strongly blue-shifted range of the spectrum. Since the most intensive bands in original dyes are ascribed to the molecular core bearing the BF2 moiety, this result can be attributed to the significant cleavage of the BF2 ring. In order to fully characterize the obtained molecules, the comprehensive computational chemistry study was performed. The influence of the intermolecular interactions for their absorption in solution was analyzed. The theoretical data entirely support the experimental outcomes.

Nature of intermolecular interaction in squaraine dimers.

Squaraine dyes are known for their particular optical properties. They exhibit intense photochemically stable fluorescence in usually (near) infra red region that can be quenched by intermolecular interactions. Moreover, even the centrosymmetric dyes feature non-zero second harmonic generation upon aggregation. Therefore, the detailed knowledge of the squaraine dye interaction nature both in homogenic aggregates and with other species present in the environment can be of importance for the design of new materials of desired properties. In the present study, interaction in squaraine dimers is investigated with quantum chemistry tools. Four structures: two stacked and two hydrogen-bonded are analyzed in terms of supermolecular approach and symmetry-adapted perturbation theory. MP2C/aug-cc-pVTZ supermolecular calculations confirm the particular stability of the stacked dimers and the favoured dispersion attraction for the long-displaced system.

Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate(iii) unit with the green → blue → red crystal color sequence.

Three new complexes forming a dynamic system and given by the following formulae: [Cu2(bpy)4Fe(ox)3]NO3·H2O 1, [Fe(bpy)3]2[Fe(ox)3]NO3·10H2O 2 and [Cu(bpy)3]2[Fe(ox)3]NO3·10H2O 3 (bpy - 2,2'-bipyridine, ox - oxalate), were synthesized from a methanol-water mixture or water, and characterized structurally, spectroscopically and magnetically. Compound 1 contains trinuclear [(bpy)2Cu(µ-ox)Fe(ox)(µ-ox)Cu(bpy)2]+ cations, while 2 and 3 can be classified as isomorphous ionic compounds, with alternately arranged hydrophobic and hydrophilic layers of mononuclear complex ions. The green crystals of 1 are perfectly stable in air, whereas in selected solvents they undergo irreversible solvent-assisted recrystallization towards red crystals of 2, which is also accompanied by the appearance of mononuclear blue copper complexes with oxalate, 2,2'-bipyridine and aqua ligands, already described in the literature. The above crystallization/recrystallization processes indicate variable solution contents. The whole effect is accelerated by both the increased temperature and day light irradiation, however, different products from the pool prevail under various conditions. The observed transformation can be understood in terms of thermodynamic and kinetic control, involving the known photo-activity of [Fe(ox)3]3- moieties and the effect of quadruple aryl embrace (QAE) on the stability of the crystal network. Considering the presence of FeIII-ox-CuII connectivity in 1 we performed detailed magnetic studies and theoretical calculations for this compound. Due to the strong asymmetry of Cu-O bonds the antiferromagnetic coupling is rather weak, with JCu-Fe being ca. -3.4 cm-1 (using Hamiltonian of the type H = -JCu-Fe(SCu1SFe + SFeSCu2) -JCu-Cu(SCu1SCu2)). We found that these values are very close to those predicted by B3LYP/6-311G* calculations.

Computational Study of the Influence of Nitrogen-Containing Unsaturated Heterocyclic Substituents on Electronic and Spectroscopic Properties of Squaraine Derivatives.

A comprehensive understanding of the influence of the different structural elements for the molecular properties is crucial for improving the material design procedures in the field of photosensitive dyes. The present study provides a detailed analysis of the influence of the number of heteroatoms (nitrogens) and the lengths of the π-electron skeleton on the one- and two-photon absorption of the symmetric squaraine dyes. Extended computational study covers the conventional vertical excitation calculations within the TD-DFT formalisms as well as several advanced single-reference methods including double excitations such as CIS(D), SAC-CI, and ADC(2). Additionally, the weaknesses of the vertical approach are investigated by including the geometry relaxation upon excitation via adiabatic and 0-0 treatment.

Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

Interaction-induced electric properties and cooperative effects in model systems.

A detailed analysis of the interaction-induced linear and non-linear axial static electric dipole properties and the interaction energy of the model HCHO(HF)(n) (n = 1, 2) complexes is carried out using the HF SCF, MP2, CCSD and CCSD(T) levels of approximation combined with a wide range of basis sets, namely the correlation-consistent basis sets of Dunning and co-workers, the polarization-consistent basis sets of Jensen, and the recently reported polarized LPol sets. The results of this study show that even the smallest among the LPol sets, the LPol-ds and LPol-dl sets, yield interaction induced axial static electric dipole properties of an accuracy comparable to that obtained with the aug-cc-pVQZ basis set. Using the LPol-ds, the LPol-dl, and the LPol-fl sets we have estimated the induced electric properties and the interaction energy of the HCHO(HF)(n) (n = 1-9) complexes, the cooperative effects in these systems, and the two-body effects. The many-body analysis shows that the two-body contributions to the induced first hyperpolarizability are not sufficient to correctly reproduce the general tendency for the changes in the property with the elongation of the polymer chain, since already for the n = 4 complex the more-than-two-body terms become dominant.

Orbit-orbit relativistic corrections to the pure vibrational non-Born-Oppenheimer energies of H(2).

We report the derivation of the orbit-orbit relativistic correction for calculating pure vibrational states of diatomic molecular systems with sigma electrons within the framework that does not assume the Born-Oppenheimer (BO) approximation. The correction is calculated as the expectation value of the orbit-orbit interaction operator with the non-BO wave function expressed in terms of explicitly correlated Gaussian functions multiplied by even powers of the internuclear distance. With that we can now calculate the complete relativistic correction of the order of alpha(2) (where alpha=1/c). The new algorithm is applied to determine the full set of the rotationless vibrational levels and the corresponding transition frequencies of the H(2) molecule. The results are compared with the previous calculations, as well as with the frequencies obtained from the experimental spectra. The comparison shows the need to include corrections higher than second order in alpha to further improve the agreement between the theory and the experiment.

Electron affinity of (7)Li calculated with the inclusion of nuclear motion and relativistic corrections.

Explicitly correlated Gaussian functions have been used to perform very accurate variational calculations for the ground states of (7)Li and (7)Li(-). The nuclear motion has been explicitly included in the calculations (i.e., they have been done without assuming the Born-Oppenheimer (BO) approximation). An approach based on the analytical energy gradient calculated with respect to the Gaussian exponential parameters was employed. This led to a noticeable improvement of the previously determined variational upper bound to the nonrelativistic energy of Li(-). The Li energy obtained in the calculations matches those of the most accurate results obtained with Hylleraas functions. The finite-mass (non-BO) wave functions were used to calculate the alpha(2) relativistic corrections (alpha=1c). With those corrections and the alpha(3) and alpha(4) corrections taken from Pachucki and Komasa [J. Chem. Phys. 125, 204304 (2006)], the electron affinity (EA) of (7)Li was determined. It agrees very well with the most recent experimental EA.

Lowest excitation energy of 9Be.

Variational calculations employing explicitly correlated Gaussian functions and explicitly including the nuclear motion [i.e., without assuming the Born-Oppenheimer (BO) approximation] have been performed to determine the lowest singlet transition energy in the 9Be atom. The non-BO wave functions were used to calculate the alpha2 relativistic corrections (alpha=1/137.035,999,679). With those corrections and with the alpha3 and alpha4 QED corrections determined previously by others, we obtained 54,677.35 cm(-1) for the 3(1)S-->2(1)S transition energy. This result falls within the error bracket for the experimental transition of 54,677.26(10) cm(-1). This is the first time an electronic transition of Be has been calculated from first principles with the experimental accuracy.

Relativistic corrections to the non-Born-Oppenheimer energies of the lowest singlet Rydberg states of 3He and 4He.

In this work the authors present an approach to calculate the leading-order relativistic corrections for ground and excited states of helium isotopomers. In the calculations they used variational wave functions expanded in terms of explicitly correlated Gaussians obtained without assuming the Born-Oppenheimer approximation.

Darwin and mass-velocity relativistic corrections in non-Born-Oppenheimer variational calculations.

The Pauli approach to account for the mass-velocity and Darwin relativistic corrections has been applied to the formalism for quantum mechanical molecular calculations that does not assume the Born-Oppenheimer (BO) approximation regarding separability of the electronic and nuclear motions in molecular systems. The corrections are determined using the first order perturbation theory and are derived for the non-BO wave function of a diatomic system expressed in terms of explicitly correlated Gaussian functions with premultipliers in the form of even powers of the internuclear distance. As a numerical example we used calculations of the transition energies for pure vibrational states of the HD(+) ion.

Darwin and mass-velocity relativistic corrections in the non-Born-Oppenheimer calculations of pure vibrational states of H2.

The Darwin and mass-velocity relativistic corrections have been calculated for all pure vibrational states of the H2 using the perturbation theory and very accurate variational wave functions obtained without assuming the Born-Oppenheimer (BO) approximation. Expansions in terms of explicitly correlated Gaussians with premultipliers in the form of even powers of the internuclear distance were used for the wave functions. With the inclusion of the two relativistic corrections to the non-BO energies the transition energies for the highest states agree more with the experimental results.

Convergence of experiment and theory on the pure vibrational spectrum of HeH(+).

Very accurate quantum mechanical calculations of the pure vibrational spectrum of the molecular ion are reported and compared with newly obtained pure vibrational transitions extracted from the available experimental data. The calculations are performed without assuming the Born-Oppenheimer approximation regarding separability of the nuclear and electronic motions and include the first order relativistic mass-velocity and Darwin corrections. For the two lowest transitions, whose experimental energies are established with the highest precision, the calculated and the experimental results show very good agreement.

Convergence of approximate two-component Hamiltonians: how far is the Dirac limit.

A systematic elimination of the off-diagonal parts of the Dirac Hamiltonian is carried out in the spirit of the Douglas-Kroll [Ann. Phys. 82, 87 1974] approach and the recently proposed infinite-order two-component method. The present approach leads to a series of approximate two-component Hamiltonians which are exact through a certain order in the external potential. These Hamiltonians are used to study the convergence pattern of approximate two-component theories. It is shown that to achieve an acceptably high accuracy for low-lying one-electron levels in heavy and superheavy systems one needs to use approximate Hamiltonians of prohibitively high order in the external potential. One can conclude that the finite-order two-component Hamiltonians are of limited usefulness in accurate relativistic calculations for heavy and superheavy systems.