Symmetry-adapted Perturbation Theory Calculations Research Articles

Taxifolin Adsorption on Nitrogenated Graphenes: Theoretical Insights

Solid-state drug delivery systems for the drug substances transport are of great importance nowadays. In the present work, the non-covalent interactions between taxifolin (Tax) and graphene as well as nitrogenated (N-doped) graphenes were systematically studied by using a wide set of theoretical techniques. Symmetry-adapted perturbation theory (SAPT0) calculations confirmed more favorable adsorption of Tax on N-doped graphenes compared to pristine graphene. It was established that dispersion interactions play the main role in the attractive interactions (>60%), whereas electrostatic and induction forces contribute only moderately to the attraction (~25% and 7–8%, respectively). Independent gradient model (IGM) analysis visually demonstrated the existence of dispersion interactions and hydrogen bonding in the studied Tax complexes. Ab initio molecular dynamics calculations indicated stability of these complexes at different temperatures. Our results show that N-doped graphenes with the enhanced interaction energy (Eint) toward Tax are promising candidates for the technical realization of the targeted drug delivery systems.

Insight into melting point differences of dinitroimidazoles and dinitropyrazoles from the perspective of intermolecular interactions.

Dinitroimidazole (DNI) and dinitropyrazole (DNP), along with their congeners, possess similar molecular structures but exhibit distinct melting points. To analyse and elucidate the fundamental reasons for property differences from the perspective of intermolecular interactions, we proposed a simplified approach named binding energy in clusters (BEC) in computing weak interactions within complex crystal systems. Based on the results of the symmetry-adapted perturbation theory (SAPT) calculations, an approximate estimation of the melting point range can be derived by taking into account the cumulative effect (energy of electrostatic, dispersion and induction terms) and repulsive effect (energy of exchange term) values. We have also proposed a formula for calculating the specific melting point, which indicates that stronger intermolecular interactions have a major impact on the melting point, while the distribution of weak interactions also affects the melting point. This work would provide an effective reference for molecular design and structure-performance analysis.

Non-covalent interactions between dihydroquercetin and arabinogalactan molecules: Theoretical study

Non-covalent interactions between Dihydroquercetin (or Taxifolin) (DHQ) and Arabinogalactan (AG) were systematically studied by using a set of theoretical techniques. Symmetry-adapted perturbation theory (SAPT0) calculations confirmed that dispersion and electrostatic interactions play the main role in attractive interactions of the DHQ/AG system (either contributes ∼40%), whereas induction forces contribute into the interaction energy (Eint) only moderately (∼15%). Independent gradient model (IGM) analysis explicitly showed existence of non-covalent interactions, including hydrogen bonds (H-bonds) in the DHQ/AG complex. Ab initio molecular dynamics studies indicated stability of DHQ/AG at room temperature. Finally, we established a stabilization of the DHQ/AG complex in solvents. Our investigations unveil the physical aspects of non-covalent interactions exist in the complex studied of two biomolecules.

Isomer Stability Dependence of Hydrogen-Bonded Benzoxazole Clusters on Solvent Molecules.

The structures of hydrogen-bonded benzoxazole clusters with methanol and ammonia, BO-(CH3OH)n (n = 1-3) and BO-(NH3)n (n = 1, 2), in a supersonic jet have been investigated by measuring the S1-S0 electronic spectra and isomer-selected vibrational spectra with the aid of quantum chemical calculations. Similar to BO-(H2O)1, two isomers of BO-(NH3)1 were observed, which form two types of hydrogen bond networks starting from the CH bond at the 2-/7-position to the nitrogen atom of BO (C2HN/C7HN). The relative stability of these isomers strongly depends on solvent molecules. Natural bond orbital analysis reveals that the OH···N hydrogen bond is dominant in BO-(H2O)1 and that intermolecular interaction between the CH group and the nitrogen atom of ammonia, especially C2H···N, is significantly enhanced, resulting in a more stable C2HN isomer. Symmetry-adapted perturbation theory calculations indicate that the dispersion interaction between the methyl group of methanol and π electron cloud on the BO ring is responsible for the extreme stability of the C7HN of BO-(CH3OH)1. Furthermore, using time-dependent density functional theory calculations, the isomer tendency of the electronic transition shifts from the monomer origin is reproduced and it is proposed that the significant blue shift in C2HN is due to the shortened C2H bond length upon electronic excitation.

A Cost Effective Scheme for the Highly Accurate Description of Intermolecular Binding in Large Complexes.

There has been a growing interest in quantitative predictions of the intermolecular binding energy of large complexes. One of the most important quantum chemical techniques capable of such predictions is the domain-based local pair natural orbital (DLPNO) scheme for the coupled cluster theory with singles, doubles, and iterative triples [CCSD(T)], whose results are extrapolated to the complete basis set (CBS) limit. Here, the DLPNO-based focal-point method is devised with the aim of obtaining CBS-extrapolated values that are very close to their canonical CCSD(T)/CBS counterparts, and thus may serve for routinely checking a performance of less expensive computational methods, for example, those based on the density-functional theory (DFT). The efficacy of this method is demonstrated for several sets of noncovalent complexes with varying amounts of the electrostatics, induction, and dispersion contributions to binding (as revealed by accurate DFT-based symmetry-adapted perturbation theory (SAPT) calculations). It is shown that when applied to dimeric models of poly(3-hydroxybutyrate) chains in its two polymorphic forms, the DLPNO-CCSD(T) and DFT-SAPT computational schemes agree to within about 2 kJ/mol of an absolute value of the interaction energy. These computational schemes thus should be useful for a reliable description of factors leading to the enthalpic stabilization of extended systems.

How Water Interacts with the NOH Group: The Rotational Spectrum of the 1:1 N,N-diethylhydroxylamine·Water Complex

The rotational spectrum of the 1:1 N,N-diethylhydroxylamine-water complex has been investigated using pulsed jet Fourier transform microwave spectroscopy in the 6.5-18.5 GHz frequency region. The most stable conformer has been detected as well as the 13C monosubstituted isotopologues in natural abundance and the 18O enriched water species, allowing to determine the nitrogen nuclear quadrupole coupling constants and the molecular structure in the vibrational ground state. The molecule has a Cs symmetry and the water lies in the bc symmetry plane forming two hydrogen bonds with the NOH frame with length: dHOH·NOH = 1.974 Å and dH2O·HON = 2.096 Å. From symmetry-adapted perturbation theory calculations coupled to atoms in molecule approach, the corresponding interaction energy values are estimated to be 24 and 13 kJ·mol-1, respectively. The great strength of the intermolecular interaction involving the nitrogen atom is in agreement with the high reactivity of hydroxylamine compounds at the nitrogen site.

Polychlorinated Biphenyls Interactions with Water—Characterization Based on the Analysis of Non-Covalent Interactions and Energy Partitioning

Although polychlorinated biphenyls (PCBs) have been long banned from use, both they and dioxins are still considered persistent organic pollutants. The reason is twofold: their relative inertness (especially to oxidation) and their ability to accumulate in fat tissue. The current study sheds light on the interactions of PCBs with water, chlorine, and chlorine dioxide. Necessary insight is gained from Atoms in Molecules (AIM) and Non-Covalent Interactions (NCI) index and analyses for the 1:1 complexes of PCBs with water and chlorine (Cl2) molecules. Further, Symmetry-Adapted Perturbation Theory (SAPT) calculations reveal the strength and nature of the intermolecular interactions, and the presence of halogen bonding is demonstrated in AIM, NCI, and SAPT studies. The stability of water, chlorine, and chlorine dioxide (ClO2) complexes with PCBs is discussed using the supramolecular MP2 approach. Finally, analysis of microsolvation shells of PCBs showed the origins of the hydrophobicity and environmental persistence of these chemicals. Our results are applicable to the sustainability of water treatment strategies providing a description of forces and interactions at the molecular level.

Strongly Bound π-Hole Tetrel Bonded Complexes between H2 SiO and Substituted Pyridines. Influence of Substituents.

Ab initio calculation at the MP2/aug-cc-pVTZ level has been performed on the π-hole based N… Si tetrel bonded complexes between substituted pyridines and H2 SiO. The primary aim of the study is to find out the effect of substitution on the strength and nature of this tetrel bond, and its similarity/difference with the N… C tetrel bond. Correlation between the strength of the N… Si bond and several molecular properties of the Lewis acid (H2 SiO) and base (pyridines) are explored. The properties of the tetrel bond are analyzed using AIM, NBO, and symmetry-adapted perturbation theory calculations. The complexes are characterized with short N… Si intermolecular distances and high binding energies ranging between -142.72 and -115.37 kJ/mol. The high value of deformation energy indicates significant geometrical distortion of the monomer units. The AIM and NBO analysis reveal significant coordinate covalent bond character of the N⋅⋅⋅Si π-hole bond. Sharp differences are also noticed in the orbital interactions present in the N⋅⋅⋅Si and N⋅⋅⋅C tetrel bonds.

Theoretical Investigation of Carbon Dioxide Adsorption on Li+-Decorated Nanoflakes.

Recently, the capture of carbon dioxide, the primary greenhouse gas, has attracted particular interest from researchers worldwide. In the present work, several theoretical methods have been used to study adsorption of CO2 molecules on Li+-decorated coronene (Li+@coronene). It has been established that Li+ can be strongly anchored on coronene, and then a physical adsorption of CO2 will occur in the vicinity of this cation. Moreover, such a decoration has substantially improved interaction energy (Eint) between CO2 molecules and the adsorbent. One to twelve CO2 molecules per one Li+ have been considered, and their Eint values are in the range from −5.55 to −16.87 kcal/mol. Symmetry-adapted perturbation theory (SAPT0) calculations have shown that, depending on the quantity of adsorbed CO2 molecules, different energy components act as the main reason for attraction. AIMD simulations allow estimating gravimetric densities (GD, wt.%) at various temperatures, and the maximal GDs have been calculated to be 9.3, 6.0, and 4.9% at T = 77, 300, and 400 K, respectively. Besides this, AIMD calculations validate stability of Li+@coronene complexes during simulation time at the maximum CO2 loading. Bader’s atoms-in-molecules (QTAIM) and independent gradient model (IGM) techniques have been implemented to unveil the features of interactions between CO2 and Li+@coronene. These methods have proved that there exists a non-covalent bonding between the cation center and CO2. We suppose that findings, derived in this theoretical work, may also benefit the design of novel nanosystems for gas storage and delivery.

Unravelling the Interactions of Magnetic Ionic Liquids by Energy Decomposition Schemes: Towards a Transferable Polarizable Force Field.

This work aims at unravelling the interactions in magnetic ionic liquids (MILs) by applying Symmetry-Adapted Perturbation Theory (SAPT) calculations, as well as based on those to set-up a polarisable force field model for these liquids. The targeted MILs comprise two different cations, namely: 1-butyl-3-methylimidazolium ([Bmim]+) and 1-ethyl-3-methylimidazolium ([Emim]+), along with several metal halides anions such as [FeCl4]−, [FeBr4]−, [ZnCl3]− and [SnCl4]2− To begin with, DFT geometry optimisations of such MILs were performed, which in turn revealed that the metallic anions prefer to stay close to the region of the carbon atom between the nitrogen atoms in the imidazolium fragment. Then, a SAPT study was carried out to find the optimal separation of the monomers and the different contributions for their interaction energy. It was found that the main contribution to the interaction energy is the electrostatic interaction component, followed by the dispersion one in most of the cases. The SAPT results were compared with those obtained by employing the local energy decomposition scheme based on the DLPNO-CCSD(T) method, the latter showing slightly lower values for the interaction energy as well as an increase of the distance between the minima centres of mass. Finally, the calculated SAPT interaction energies were found to correlate well with the melting points experimentally measured for these MILs.

Sumanene as a delivery system for 5-fluorouracil drug – DFT, SAPT and MD study

In this work, density functional theory (DFT) and symmetry-adapted perturbation theory (SAPT) calculations, together with molecular dynamics (MD) simulations, were used to study the interaction between sumanene molecule and 5-fluorouracil (5-FU). 5FU is a known and frequently employed cytostatic drug. To better understand the effects of the curvature of sumanene, we have also considered the interaction between 5-FU and coronene, a sumanene's relative with planar geometry. DFT calculations at B3LYP-D3/6-31G(d,p) level of theory were used to obtain information on binding energies and identify and visualize the noncovalent interactions between the 5-FU and the sumanene/coronene. DFT calculations revealed that 5-FU binds to sumanene's concave side much stronger than to its convex side. The strengths of noncovalent interactions explained the obtained trends in the binding energies. The SAPT0 calculations helped reveal the essential physical contributions to the interaction energies. The importance of the electrostatic component was emphasized in the case of adsorption from sumanene's concave side. Molecular electrostatic potential was compared between the sole molecules and complexes. Simulation of the UV spectra was performed to evaluate whether the binding of 5FU to sumanene could be tracked and monitored by UV spectroscopy. Last but not least, MD simulations were performed to check the influence of temperature on the interaction between sumanene and 5FU. It was established that an increase in temperature significantly decreases the interaction between sumanene and 5FU.

Hydrogen adsorption on pillar[6]arene: A computational study

Abstract A systematical theoretical work on physisorption of H2 molecules by both pristine and Li+-decorated per-hydroxylated pillar[6]arene (PPA ) in the gas phase has been performed by using density functional theory (DFT) and 0th order symmetry-adapted perturbation theory calculations (SAPT0). A complementary analysis using ab initio molecular dynamics (AIMD), atoms-in-molecules (AIM) and independent gradient model (IGM) methods has also been done. Our calculations have shown that H2 molecules can be adsorbed favorably inside the PPA hollow compared with pristine graphene. However, the obtained magnitudes of adsorption energy (Ead ) fall outside the optimal range of energies for hydrogen storage . On the other hand, Li + decoration has drastically improved both Ead and quantity of adsorbed hydrogen molecules. It has been established that each cation center is capable of uptaking from one to five H2 molecules per Li+, and their Ead are in the range from −3.57 to −5.40 kcal/mol. SAPT0 calculations have indicated the prevalence of London dispersion or induction forces in the cases of adsorption inside PPA hollows and on Li+, respectively. AIM and IGM analyses have exhibited that a non-covalent bonding exists between Li+ and H2, and the adsorbed H2 molecules are undissociated. AIMD simulations allow estimating gravimetric densities (GD) at various temperatures, and the maximal GD have been calculated to be 6.0, 4.8, and 3.8% at T = 77, 233, and 300 K, respectively. Besides this, AIMD calculations validate stability of studied structures and the quantity of hydrogen adsorbed. We believe that some of the considerations derived herein establish the high potential of the studied PPA models for hydrogen storage.

Seeking the Source of Catalytic Efficiency of Lindane Dehydrochlorinase, LinA.

Herein we present the results of an in-depth simulation study of LinA and its two variants. In our analysis, we combined the exploration of protein conformational dynamics with and without bound substrates (hexachlorocyclohexane (HCH) isomers) performed using molecular dynamics simulation followed by the extraction of the most frequently visited conformations and their characteristics with a detailed description of the interactions taking place in the active site between the respective HCH molecule and the first shell residues by using symmetry-adapted perturbation theory (SAPT) calculations. A detailed investigation of the conformational space of LinA substates has been accompanied by description of enzymatic catalytic steps carried out using a hybrid quantum mechanics/molecular mechanics (QM/MM) potential along with the computation of the potential of mean force (PMF) to estimate the free energy barriers for the studied transformations: dehydrochlorination of γ-, (−)-α-, and (+)-α-HCH by LinA-type I and -type II variants. The applied combination of computational techniques allowed us not only to characterize two LinA types but also to point to the most important differences between them and link their features to catalytic efficiency each of them possesses toward the respective ligand. More importantly it has been demonstrated that type I protein is more mobile, its active site has a larger volume, and the dehydrochlorination products are stabilized more strongly than in the case of type II enzyme, due to differences in the residues present in the active sites. Additionally, interaction energy calculations revealed very interesting patterns not predicted before but having the potential to be utilized in any attempts of improving LinA catalytic efficiency. On the basis of all these observations, LinA-type I protein seems to be more preorganized for the dehydrochlorination reaction it catalyzes than the type II variant.

Comparison between Chlorine-Shared and π-Halogen Bonds Involving Substituted Phosphabenzene and ClF Molecules.

Ab initio MP2/aug-cc-pVTZ calculations have been carried out in order to study the nature of P···Cl halogen bonding interaction between a phosphorus atom in an aromatic ring in para-substituted phosphabenzene (PPBZ) and ClF molecule. The interaction of PPBZ with ClF results in two different types of complexes: (i) complex formation through the chlorine-shared halogen bond (T1-X-PPBZ·ClF) and (ii) complex formation via halogen−π interaction (T2-X-PPBZ·ClF). T1-X-PPBZ·ClF complexes are found to be more stable than the T2-X-PPBZ·ClF complexes. This work also presents a general criterion to distinguish a chlorine-shared halogen bond from a traditional halogen bond and sheds light on the formation of the chlorine-shared halogen bond. The binding energy of T1-X-PPBZ·ClF complexes correlates well with the negative electrostatic potential of the P atom and PA value of the substituted PPBZ. The properties of both T1-X-PPBZ·ClF and T2-X-PPBZ·ClF complexes are analyzed using atom-in-molecule, natural bond orbital, and symmetry-adapted perturbation theory calculations. The variation of the Cl–F bond distances and the redshifts of the ν(ClF) vibration resulting from the interaction with PPBZs are discussed.

Microsolvation of myrtenal studied by microwave spectroscopy highlights the role of quasi-hydrogen bonds in the stabilization of its hydrates.

Hydrates of myrtenal (C10H14O) · (H2O)n (n = 1, 2, 3) were experimentally investigated in a molecular jet using a cavity-based Fourier transform microwave spectrometer in the 2.6 GHz-15 GHz frequency range. The assignment of the spectra was made possible, thanks to computationally optimized structures at the B3LYP-D3BJ/def2-TZVP and MP2/6-311++G(d,p) levels using the Gaussian 16 software. The spectra of two mono- and two dihydrates and those of the lowest energy conformer among the two expected trihydrates could be assigned. A similar study replacing normal water by 18O labeled water allowed the identification of the spectra of all possible isotopomers, leading to the calculation of the substitution coordinates of water oxygen atoms and that of the effective structure of the water molecule arrangements around myrtenal, except for the trihydrate. The structure of the latter species was nevertheless confirmed by the analysis of the spectrum of the isotopomer with three H2 18O molecules. The computational rotational constants and structural parameters were found quite close to the experimental ones at the density functional theory B3LYP-GD3BJ/def2-TZVP and ab initio MP2/6-311++G(d,p) levels. Symmetry adapted perturbation theory calculations reveal that the aldehyde hydrogen atom strongly interacts with water oxygen atoms in the case of di- and trihydrates.

Assessment of SAPT(DFT) with meta-GGA functionals

This work examines the suitability of meta-GGA functionals for symmetry-adapted perturbation theory (SAPT) calculations. The assessment is based on the term-by-term comparison with the benchmark SAPT variant based on coupled-cluster singles and doubles description of monomers, SAPT(CCSD). Testing systems include molecular complexes ranging from strong to weak and the He dimer. The following nonempirical meta-GGAs are examined: TPSS, revTPSS, MVS, SCAN, and SCAN0 with and without the asymptotic correction (AC) of the exchange-correlation potential. One range-separated meta-GGA functional, LC-PBETPSS, is also included. The AC-corrected pure meta-GGAs (with the exception of MVS) represent a definite progress in SAPT(DFT) compared to pure GGA, such as PBEAC, with their more consistent predictions of energy components. However, none of the meta-GGAs is better than the hybrid GGA approach SAPT(PBE0AC). The SAPT(DFT) electrostatic energy offers the most sensitive probe of the quality of the underlying DFT density. Both SCAN- and TPSS-based electrostatic energies agree with reference to within 5% or better which is an excellent result. We find that SCAN0 can be used in SAPT without the AC correction. The long-range corrected LC-PBETPSS is a reliable performer both for the components and total interaction energies.

Non-covalent interactions and their impact on the complexation thermodynamics of noble gases with methanol.

Accurate ab initio calculations provide the reliable information needed to study the potential energy surfaces that control the non-covalent interactions (NCIs) responsible for the formation of weak van der Waals complexes. In this work, relying on the state of the art method for NCI computations, namely symmetry adapted perturbation theory (SAPT), we calculated the potential energy curves for the interaction of noble gases (Ng = He, Ne, Ar and Kr) with methanol in three different interaction sites to account for orientational anisotropy of the interaction potential. Different levels of the SAPT and basis set were employed to disclose the nature of the stabilizing forces acting upon formation of the Ng-CH3OH adducts. SAPT-derived NCIs indicate that dispersion forces are indeed the dominating component of the total energy, but also that induction and electrostatic effects are important to counterbalance the steric repulsions. By solving the Radial Nuclear Schrödinger Equation for the complexes, we also determined the rovibrational structure of the interaction wells to extract invaluable information about the thermodynamic stability of the adducts and how different temperature conditions affect the structure of the dimers. Although SAPT calculations reveal net attractive forces, these do not afford a spontaneous complexation process even at temperatures as low as 40 K.

CO2 Capture on Functionalized Calixarenes: A Computational Study

High carbon emissions have shown a strong correlation with rising global temperatures as the world's climate undergoes a dramatic shift. Work to mitigate the potential damage using materials such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and polymer membranes (PMs) has proven successful in small-scale approaches; however, research is still being performed to enhance the capabilities of these materials for use at an industrial scale. One strategy for increasing performance is to embed these materials with CO2-philic molecules, which enhance selective binding over other gases. Calixarenes are promising candidates due to their large chalice shape, which allows for the possibility to bind multiple CO2 molecules per site. In this study, a dataset including 40 functionalized calixarene structures and one unfunctionalized (bare) calixarene was constructed with an automated, high-throughput structure generation through directed modifications to a molecular scaffold. A conformational search based on molecular mechanics allowed the faster determination of optimal binding energies for a vast array of chemical functional groups with less computational effort. Density functional theory and symmetry-adapted perturbation theory calculations were performed for the exploration of their interactions with CO2. Our work has identified new organic cages with increased CO2-philicity. In four cases, CO2 binding is stronger than 9.0 kcal/mol and very close to the targets set by previous studies. The nature of the noncovalent interactions for these cases is analyzed and discussed. Conclusions from this study can aid synthetic efforts for the next generation of functional materials.

A DFT and MD study of reactive, H2 adsorption and optoelectronic properties of graphane nanoparticles – An influence of boron doping

Structural, reactive, H2 adsorption and charge transfer properties of graphane nanoparticles modified with boron atom have been investigated using the combination of density functional theory (DFT) calculations and molecular dynamics (MD) simulations. Studies of reactivity encompassed calculations of molecular electrostatic potential (MEP) and average local ionization energy (ALIE) descriptors. It has been demonstrated by these quantum-molecular descriptors that reactivity of studied systems significantly increases in the near vicinity of boron dopants. Adsorption properties of studied graphane and its derivative nanoparticles have been performed towards the hydrogen molecules, in order to assess the potential of studied structures in the area of clean energy sources. Results indicate that introduction of boron atoms greatly improves the H2 binding energies. Symmetry-adapted perturbation theory (SAPT) calculations enabled us to decompose the interaction energy to physical contributions and to better understand the influence of boron atoms to the H2 adsorption properties. Charge transfer rates and charge mobilities have been calculated according to Marcus semi-empiric approach. Optoelectronic properties of studied nanostructures have been compared to that of pentacene molecule, in order to further draw attention to their potential for practical applications in materials science area. The influence of size of the graphane nanoparticles was also taken into account and calculations show that both reorganization energies and ΔE(S1−T1) parameter decrease with the increase in size. In case of the largest pristine graphane nanoparticle considered in this work, the electron reorganization energy is lower than in case of the pentacene, while ΔE(S1−T1) parameter has very low value of just 0.05 eV.

Transferable, Polarizable Force Field for Ionic Liquids.

A general, transferable, polarizable force field for molecular simulation of ionic liquids (ILs) and their mixtures with molecular compounds is developed. This polarizable model is derived from the widely used CL&P fixed-charge force field that describes most families of ILs, in a form compatible with OPLS-AA, one of the major force fields for organic compounds. Models for ILs with fixed, integer-ionic charges lead to pathologically slow dynamics, a problem that is corrected when polarization effects are included explicitly. In the model proposed here, Drude-induced dipoles are used with parameters determined from atomic polarizabilities. The CL&P force field is modified upon inclusion of the Drude dipoles to avoid double-counting of polarization effects. This modification is based on first-principles calculations of the dispersion and induction contributions to the van der Waals interactions using symmetry-adapted perturbation theory (SAPT) for a set of dimers composed of positive, negative, and neutral fragments representative of a wide variety of ILs. The fragment approach provides transferability, allowing the representation of a multitude of cation and anion families, including different functional groups, without the need to reparametrize. Because SAPT calculations are expensive, an alternative predictive scheme was devised, requiring only molecular properties with a clear physical meaning, namely, dipole moments and atomic polarizabilities. The new polarizable force field, CL&Pol, describes a broad set of ILs and their mixtures with molecular compounds and is validated by comparisons with experimental data on density, ion diffusion coefficients, and viscosity. The approaches proposed here can also be applied to the conversion of other fixed-charge force fields into polarizable versions.