Interaction-induced Electric Properties Research Articles

Interaction-induced electric (hyper)polarizability in the dihydrogen-neon pair: basis set and electron correlation effects.

We investigated the interaction (hyper)polarizability of neon-dihydrogen pairs by performing high-level ab initio calculations with atom/molecule-specific, purpose-oriented Gaussian basis sets. We obtained interaction-induced electric properties at the SCF, MP2, and CCSD levels of theory. At the CCSD level, for the T-shaped configuration, around the respective potential minimum of 6.437 a0, the interaction-induced mean first hyperpolarizability varies for 5 < R/a0 < 10 as[Formula: see text]Again, at the CCSD level, but for the L-shaped configuration around the respective potential minimum of 6.572 a0, this property varies for 5 < R/a0 < 10 as[Formula: see text] Graphical Abstract Interaction-induced mean dipole polarizability ([Formula: see text]) for the T-shaped configuration of H2-Ne calculated at the SCF, MP2, and CCSD levels of theory.

Carbon dioxide interacting with rare gases: Insights from high-level ab initio calculations of polarizability and hyperpolarizability effects

We have obtained a quantitative, synthetic picture of the interaction-induced (hyper)polarizability in the sequence of the weakly bound complexes CO2⋯Rg, Rg=He, Ne, Ar, Kr, Xe. The properties are calculated from finite-field Møller-Plesset perturbation theory and coupled cluster calculations. We rely on flexible, prepared purpose-oriented atom- and molecule-specific basis set of Gaussian-type functions. We obtained interaction-induced electric properties for both the most stable T-shaped configuration and the less stable L-shaped one. Our interaction-induced first and second hyperpolarizabilities for the most stable (T-shaped) configurations, at the second order Møller-Plesset perturbation theory level are β¯int/e3a03Eh-2 (CO2⋯Rg)=1.14 (He), 2.02 (Ne), 2.50 (Ar), 0.50 (Kr) and −5.32 (Xe). For the second hyperpolarizability at the same level of theory γ¯int/e4a04Eh-3 (CO2⋯Rg)=−11.66 (He), −25.88 (Ne), −108.16 (Ar), −206.75 (Kr) and −460.42 (Xe). In the vicinity of the equilibrium configuration, with the Rg atom displaced on the x axis for T-shaped configuration, the first hyperpolarizability changes as dβ¯dRee3a02Eh-2 (CO2⋯Rg)=−1.07 (He), −1.86 (Ne), −0.71 (Ar), 2.65 (Kr) and 9.96 (Xe). For the second hyperpolarizability dγ‾dRee4a03Eh-3 (CO2⋯Rg)=7.94 (He), 20.34 (Ne), 65.00 (Ar), 118.48 (Kr) and 239.84 (Xe).

On the physical origins of interaction-induced vibrational (hyper)polarizabilities.

This paper presents the results of a pioneering exploration of the physical origins of vibrational contributions to the interaction-induced electric properties of molecular complexes. In order to analyze the excess nuclear relaxation (hyper)polarizabilities, a new scheme was proposed which relies on the computationally efficient Bishop-Hasan-Kirtman method for determining the nuclear relaxation contributions to electric properties. The extension presented herein is general and can be used with any interaction-energy partitioning method. As an example, in this study we employed the variational-perturbational interaction-energy decomposition scheme (at the MP2/aug-cc-pVQZ level) and the extended transition state method by employing three exchange-correlation functionals (BLYP, LC-BLYP, and LC-BLYP-dDsC) to study the excess properties of the HCN dimer. It was observed that the first-order electrostatic contribution to the excess nuclear relaxation polarizability cancels with the negative exchange repulsion term out to a large extent, resulting in a positive value of Δα(nr) due to the contributions from the delocalization and the dispersion terms. In the case of the excess nuclear relaxation first hyperpolarizability, the pattern of interaction contributions is very similar to that for Δα(nr), both in terms of their sign as well as relative magnitude. Finally, our results show that the LC-BLYP and LC-BLYP-dDsC functionals, which yield smaller values of the orbital relaxation term than BLYP, are more successful in predicting excess properties.

On the Origins of Large Interaction-Induced First Hyperpolarizabilities in Hydrogen-Bonded π-Electronic Complexes

In this article we elucidate the origins of interaction-induced linear and nonlinear electro-optic properties of model hydrogen-bonded π-electronic complexes. In particular we report on contributions due to various interaction energy terms to excess dipole moments (Δμ), electric dipole polarizabilities (Δα), and first hyperpolarizabilities (Δβ), focusing on the latter. The analysis of intermolecular interaction-induced electric properties is performed for selected model systems including quasi-linear dimers of urea, diformamide, 4-pyridone, 4-nitroaniline, and the complex of hydrogen fluoride with nitroacetylene. The nature of intermolecular interactions as well as of the Δμ and Δα is very similar in all studied complexes. However, partitioning of Δβ into physically well-defined components reveals that the origins of this term, the magnitude of which is often comparable to the hyperpolarizabilities of isolated monomers, are different in each case. Our results indicate that, even though hydrogen bonding usually diminishes the nonlinear response of interacting species, the first hyperpolarizability of complexes with the nitro group acting as a proton acceptor is substantially increased, essentially due to field-induced changes of electrostatic interactions between subsystems. However, in the remaining complexes the origins of Δβ are much more involved. Even though at large intermolecular separations the origins of interaction-induced electric properties are essentially due to the field-induced electrostatic and induction interactions, in the vicinity of van der Waals minimum the overlap effects cannot be neglected since they may substantially alter the predicted excess properties or even determine their magnitude and sign. On the other hand the Δβ contribution due to dispersion interactions is usually negligible. Interestingly, the values of interaction-induced first hyperpolarizability in some cases depend strongly on the intermolecular separation in the vicinity of equilibrium geometry.

How does the Boys and Bernardi counterpoise correction scheme affects the calculated interaction-induced electric properties? Model hydrogen-bonded systems as a case study

A comprehensive analysis of the influence of the Boys and Bernardi counterpoise correction on the calculated incremental static electric properties (dipole moment, polarizability and first-order hyperpolarizability) has been carried out for selected hydrogen-bonded complexes. The model dimeric systems consisting of HF, H3N and H2CO molecules have been chosen as a case study. Calculations of components of the static electric dipole properties using the diffuse Dunning’s basis sets aug-cc-pVXZ (X=D, T, Q, 5) and d-aug-cc-pVXZ (X=D, T, Q) have been performed employing various ab initio methods: HF, MP2, MP2-F12, CCSD, CCSD(T) and CCSD(T)-F12.

New basis sets for the evaluation of interaction-induced electric properties in hydrogen-bonded complexes

Interaction-induced static electric properties, that is, dipole moment, polarizability, and first hyperpolarizability, of the CO-(HF)(n) and N(2)-(HF)(n), n = 1-9 hydrogen-bonded complexes are evaluated within the finite field approach using the Hartree-Fock, density functional theory, Møller-Plesset second-order perturbation theory, and coupled cluster methods, and the LPol-n (n = ds, dl, fs, fl) basis sets. To compare the performance of the different methods with respect to the increase of the complex size, we consider as model systems linear chains of the complexes. We analyze the results in terms of the many-body and cooperative effects.

On the Calculations of Interaction Energies and Induced Electric Properties within the Polarizable Continuum Model

In this work we investigate the influence of a polarizable environment on the interaction energies and the interaction-induced (excess) static electric dipole properties for the selected model hydrogen-bonded complexes. The excess properties were estimated for water and hydrogen fluoride dimers using the supermolecular approach and assuming the polarizable continuum model (PCM) as a representation of the polarizable environment. We analyze in this context the performance of the counterpoise correction and the consequences of various possible monomer cavity choices. The polarizable environment reduces the absolute magnitudes of interaction energies and interaction-induced dipole moments, whereas an increase is observed for the absolute magnitudes of induced polarizabilities and first hyperpolarizabilities. Our results indicate that the use of either monomeric (MC) or dimeric (DC) cavities in calculations of monomer properties does not change qualitatively the resultant excess properties. We conclude that the DC scheme is more consistent with the definition of the interaction energy and consequently also the interaction-induced property, whereas the MC scheme corresponds to the definition of stabilization energy. Our results indicate also a good performance of the counterpoise correction scheme for the self-consistent methods in the case of all studied properties.

On the potential application of DFT methods in predicting the interaction-induced electric properties of molecular complexes. Molecular H-bonded chains as a case of study

A detailed analysis of the selected DFT functionals for the calculations of interaction-induced dipole moment, polarizability and first-order hyperpolarizability has been carried out. The hydrogen-bonded model chains consisting of HF, H2CO and H3N molecules have been chosen as a case study. The calculations of the components of the static electric properties using the diffuse Dunning’s basis set (aug-cc-pVDZ) have been performed employing different types of density functionals (B3LYP, LC-BLYP, PBE0, M06-2X and CAM-B3LYP). Obtained results have been compared with those gained at the CCSD(T) level of theory. The counterpoise correction scheme, namely site-site function counterpoise, has been applied in order to eliminate basis set superposition error. The performed tests allow to conclude that the DFT functionals can provide a useful tool for prediction of the interaction-induced electric properties, however a caution has to be urged to their decomposition to the two- and many-body terms. Figure Hydrogen-bonded model chains consisting of HF, H2CO and H3N molecules

Interaction-induced electric properties in Kr–Ne from ab initio and DFT calculations. Is there a discrepancy between theory and experiment for the dipole moment?

We have obtained interaction-induced dipole moment, dipole polarizability and first hyperpolarizability curves for the KrNe rare gas heterodiatom using ab initio and DFT methods and a large, flexible atom-specific basis set. We have carefully examined the agreement between the two groups of theoretical methods. Although the experimentally deduced values for the dipole moment differ substantially, our best ab initio results are in very satisfactory agreement with the range suggested by the experimental estimates.

Comparison of high-level post-Hartree–Fock and DFT methods on the calculation of interaction-induced electric properties of Kr–He

We have calculated the interaction dipole moment and polarizability of the Kr–He pair with high-level ab initio methods and density functional theory (DFT) methods relying on a flexible, atom-specific basis set. High-order electron correlation effects are of some importance for internuclear separations up to the minimum of the interaction potential (R e). At short distances the performance of ab initio and DFT methods is quite distinct. At the experimental separation R e = 6.97309 a 0 and the highest level of theory CCSD(T), we estimate the interaction dipole moment, mean and anisotropy of the polarizability as μ = 0.0017 ea 0, α ¯ = - 0.019 and Δ α = 0.353 e 2 a 0 2 E h - 1 , respectively. The derivatives of interaction properties are d μ dR e = - 0.0028 e, d α ¯ dR e = 0.036 and d Δ a dR e = - 0.073 e 2 a 0 E h - 1 . The DFT methods offer a reasonable picture of the dipole moment and mean polarizability at R e but overestimate the magnitude of the anisotropy and its derivative.

Assessment of DFT functionals for the calculation of interaction-induced electric properties of molecular complexes

A detailed evaluation of DFT methods for the calculations of the interaction-induced electric properties has been performed. H-bonded model complexes (HF⋯HF, H2O⋯H2O and H2CO⋯HF) have been taken for investigation. The calculations of the components of the static electric properties have been carried out employing different types of density functionals. Procured results have been compared with those obtained at the CCSD (T) level of theory. The diffuse Dunning’s and Jensen’s basis sets of increasing size (aug-cc-pVXZ and aug-pc-Y, respectively) have been tested. The counterpoise correction scheme has been applied in order to eliminate basis set superposition error. The present contribution shows that DFT allows to well-reproduce the CCSD (T) results for the interaction-induced dipole moment and (hyper) polarizability and PBE0 performs best of all the analyzed functionals, although no definite answer can be given of which functional is best in general.

Importance of electron correlation effects and basis set superposition error in calculations of interaction energies and interaction-induced electric properties in hydrogen-bonded complexes: a model study

A detailed study of the interaction energies and interaction-induced electric dipole properties in model linear hydrogen cyanide complexes (HCN) m (m = 2–4) is carried out within the finite field HF SCF, MP2, CCSD and CCSD(T) approximations using the recently developed LPol-n (n = ds, fs, dl, fl) basis sets. The importance of high-order correlation effects and the basis set superposition error is evaluated. To correct for the latter is crucial for obtaining accurate interaction energy values, but the error can safely be neglected in the estimation of induced electric properties when the LPol-n (n = ds, fs, dl, fl) basis sets are used. Correlation effects are important in the evaluation of both the interaction energies and the induced electric properties of the systems.

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.

On the basis set superposition error in supermolecular calculations of interaction-induced electric properties: many-body components

In the present paper we analyze basis set superposition error (BSSE) removal methods from many-body components of interaction-induced electric properties. The Valiron–Mayer function counterpoise (VMFC), site–site function counterpoise (SSFC) and TB methods have been employed in order to obtain the incremental optical components of linear hydrogen fluoride clusters (HF)n, where n = {3,4}. Following Mierzwicki and Latajka, who have performed similar calculations for the interaction energy, we compare those three methods of eliminating BSSE using several Dunning’s correlation consistent basis sets.

On decomposition of interaction-induced electric properties of HF dimer

Interaction energy in the linear HF dimer is calculated by means of the variational–perturbational scheme. Interaction-induced electric properties: dipole moment, polarizability and first-order hyperpolarizability are decomposed into the terms of physical meaning as the corresponding derivatives of the interaction energy components. The distance dependence of the particular contributions to the interaction energy as well as to the electric properties is reported.

On the Many-Body Components of Interaction-Induced Electric Properties: Linear Fluoroacetylene Trimer as a Case Study.

Results of many-body analysis of interaction-induced linear and non-linear optical properties are discussed. In particular the size of the basis set superposition error in many-body components of interaction-induced electric properties is examined. In order to eliminate the basis set superposition error the site-site function counterpoise method has been incorporated. The linear fluoroacetylene trimer has been chosen as a model system. In addition the results for two types of geometries (fixed and relaxed one) have been compared in order to determine whether the structural changes influence strongly the components of interaction-induced electric properties.

On the influence of confinement effects on electric properties: An ab initio study

Confinement effects on the electric properties of model system are investigated. The system under consideration is 1-cyanoethyne molecule surrounded by helium atoms arranged in the shape of armchair nanotube. Decreasing the diameter of the helium nanotube corresponds to the simulation of the confinement effects on the enclosed system. The decomposition of the interaction energy and interaction-induced electric properties reveals that dispersion terms plays an important role in the interaction between subsystems. It is observed that the absolute values of dipole moment and first-order hyperpolarizability decrease as a function of the tube radius.

Relativistic effects on interaction-induced electric properties of weakly interacting systems: The HF…AuH dimer

The relativistic effect on interaction-induced dipole moment and polarizability in the HF…AuH dimer is studied in the framework of the long-range perturbation theory model and by using the supermolecular approach. The perturbation treatment is limited to the lowest multipole-expanded form known as the dipole–induced-dipole (DID) approximation. Although the long-range DID model may be useful in elucidating the origin of the relativistic effect on interaction-induced electric properties, it fails to predict the correct magnitude of this effect for all but very large separations between the two subsystems. At intermediate monomer separations the supermolecular model predicts a substantial relativistic contribution to interaction-induced dipole moments and a rather moderate relativistic effect on induced polarizabilities. It has also been found that the vibrational contribution to the interaction-induced polarizability estimated in the double harmonic approximation may dominate over the changes in the pure electronic term. However, sufficiently accurate calculations of the vibrational contribution to electric properties of a weakly bound dimer, which would confirm this finding, appear to be unlikely at present.

Polarized basis sets for high-level-correlated calculations of molecular electric properties

The first-order polarized basis sets are generated for Zn, Cd, and Hg and their performance is tested in high-level-correlated calculations of electric dipole polarizabilities of these atoms. The present results calculated at the level of the non-relativistic CCSD(T) approximation with 12 explicitly correlated electrons are: 40.4 a.u. for Zn, 56.3 a.u. for Cd, and 58.0 a.u. for Hg. Upon including the relativistic and electron correlation-relativistic corrections within the quasirelativistic scheme based on the mass-velocity and Darwin terms these values are reduced to 37.9 a.u., 47.6 and 31.8 a.u., respectively. The derived polarized basis sets have been also used for the evaluation of the dipole polarizability of singly and doubly positive ions of the group IIb elements and are recommended for calculations of interaction energies and interaction-induced electric properties in both neutral and charged systems.