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Polarizability
Kinds of Polarizability Selected AbstractsPolarizability, Susceptibility, and Dielectric Constant of Nanometer-Scale Molecular Films: A Microscopic ViewADVANCED FUNCTIONAL MATERIALS, Issue 13 2010Amir Natan Abstract The size-dependence of the polarizability, susceptibility, and dielectric constant of nanometer-scale molecular layers is explored theoretically. First-principles calculations based on density functional theory are compared to phenomenological modeling based on polarizable dipolar arrays for a model system of organized monolayers composed of oligophenyl chains. Size trends for all three quantities are primarily governed by a competition between out-of-plane polarization enhancement and in-plane polarization suppression. Molecular packing density is the single most important factor controlling this competition and it strongly affects the bulk limit of the dielectric constant as well as the rate at which it is approached. Finally, the polarization does not reach its "bulk" limit, as determined from the Clausius,Mossotti model, but the susceptibility and dielectric constant do converge to the correct bulk limit. However, whereas the Clausius,Mossotti model describes the dielectric constant well at low lateral densities, finite size effects of the monomer units cause it to be increasingly inaccurate at high lateral densities. [source] Electronic Structure of Self-Assembled Monolayers on Au(111) Surfaces: The Impact of Backbone PolarizabilityADVANCED FUNCTIONAL MATERIALS, Issue 23 2009LinJun Wang Abstract Modifying metal electrodes with self-assembled monolayers (SAMs) has promising applications in organic and molecular electronics. The two key electronic parameters are the modification of the electrode work function because of SAM adsorption and the alignment of the SAM conducting states relative to the metal Fermi level. Through a comprehensive density-functional-theory study on a series of organic thiols self-assembled on Au(111), relationships between the electronic structure of the individual molecules (especially the backbone polarizability and its response to donor/acceptor substitutions) and the properties of the corresponding SAMs are described. The molecular backbone is found to significantly impacts the level alignment; for molecules with small ionization potentials, even Fermi-level pinning is observed. Nevertheless, independent of the backbone, polar head-group substitutions have no effect on the level alignment. For the work-function modification, the larger molecular dipole moments achieved when attaching donor/acceptor substituents to more polarizable backbones are largely compensated by increased depolarization in the SAMs. The main impact of the backbone on the work-function modification thus arises from its influence on the molecular orientation on the surface. This study provides a solid theoretical basis for the fundamental understanding of SAMs and significantly advances the understanding of structure,property relationships needed for the future development of functional organic interfaces. [source] Fukui functions for atoms and ions: Polarizability justified approachINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2010Szarek Abstract Recently proposed Fukui function has been tested for a collection of atoms and atomic ions. The key point of the analysis is an approximation for the softness kernel, as an extended and parameterized version of the local approximation s(r,r,) = s(r),(r , r,). The new Fukui functions lead to exact reproduction of global electronic dipole polarizability and atomic softness. The global hardness calculated with the classic definition using new Fukui functions and the hardness kernel |r , r,|,1 matches the , = I , A value with linear correlation superior to any other published hitherto. Applied approximations for the softness and hardness kernels were proved to be in perfect coherence. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Rough and Fine Tuning of Metal Work Function via Chemisorbed Self-Assembled MonolayersADVANCED MATERIALS, Issue 10-11 2009Maria L. Sushko The sign of the monolayer-induced metal work function change is mainly determined by the relative polarizabilities of the head- and tail-groups of the molecules, while its magnitude can be finely tuned by adjusting the strength of depolarization in the SAM, which depends on the choice of length of the nonpolarizable spacer between the polar groups. [source] Range and strength of intermolecular forces for van der Waals complexes of the type H2Xn -Rg, with X = O, S and n = 1,2INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2010Patrícia R. P. Barreto Abstract This study is intended as a continuation of previous experimental and theoretical works on the systems H2O-Rg, H2S-Rg, H2O2 -Rg, and H2S2 -Rg, where Rg = He, Ne, Ar, Kr, Xe. For the H2O-Rg and H2S-Rg systems, molecular and atomic polarizabilities have been calculated and from them, using phenomenological correlation formulas modeling the dispersion-repulsion (van der Waals) forces, the isotropic interaction parameters have been determined and compared with experimental data from this laboratory. For the H2O2 -Rg and H2S2 -Rg systems, the molecular polarizabilities have been calculated and used in correlation formulas to predict well depths and positions of van der Waals forces and a comparison made with the corresponding potential energy surfaces calculated in previous works. The approach correctly predicts the interaction parameters, except for H2O and H2O2 with the heavier rare gases. The correlation formulas have been then extended to include an attractive induction contribution accounting for the interaction between the permanent molecular dipole moment and the instantaneous induced atomic dipole moment, to improve the predicted parameters for H2O and H2O2 -Ar, Kr and Xe. The agreement with experimental and theoretical data is improved but the predicted data still underestimate the interaction. This is probably due to the presence of a significant non van der Waals contribution to the interaction for the heavier gases, as suggested by analogy with the previously studied water-Rg case. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] MP2, DFT-D, and PCM study of the HMB,TCNE complex: Thermodynamics, electric properties, and solvent effects,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 9 2008Ondrej Kysel Abstract Geometry, thermodynamic, and electric properties of the ,-EDA complex between hexamethylbenzene (HMB) and tetracyanoethylene (TCNE) are investigated at the MP2/6-31G* and, partly, DFT-D/6-31G* levels. Solvent effects on the properties are evaluated using the PCM model. Fully optimized HMB,TCNE geometry in gas phase is a stacking complex with an interplanar distance 2.87 × 10,10 m and the corresponding BSSE corrected interaction energy is ,51.3 kJ mol,1. As expected, the interplanar distance is much shorter in comparison with HF and DFT results. However the crystal structures of both (HMB)2,TCNE and HMB,TCNE complexes have interplanar distances somewhat larger (3.18 and 3.28 × 10,10 m, respectively) than our MP2 gas phase value. Our estimate of the distance in CCl4 on the basis of PCM solvent effect study is also larger (3.06,3.16 × 10,10 m). The calculated enthalpy, entropy, Gibbs energy, and equilibrium constant of HMB,TCNE complex formation in gas phase are: ,H0 = ,61.59 kJ mol,1, ,S = ,143 J mol,1 K,1, ,G0 = ,18.97 kJ mol,1, and K = 2,100 dm3 mol,1. Experimental data, however, measured in CCl4 are significantly lower: ,H0 = ,34 kJ mol,1, ,S = ,70.4 J mol,1 K,1, ,G0 = ,13.01 kJ mol,1, and K = 190 dm3 mol,1. The differences are caused by solvation effects which stabilize more the isolated components than the complex. The total solvent destabilization of Gibbs energy of the complex relatively to that of components is equal to 5.9 kJ mol,1 which is very close to our PCM value 6.5 kJ mol,1. MP2/6-31G* dipole moment and polarizabilities are in reasonable agreement with experiment (3.56 D versus 2.8 D for dipole moment). The difference here is due to solvent effect which enlarges interplanar distance and thus decreases dipole moment value. The MP2/6-31G* study supplemented by DFT-D parameterization for enthalpy calculation, and by the PCM approach to include solvent effect seems to be proper tools to elucidate the properties of ,-EDA complexes. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Comparative study of unscreened and screened molecular static linear polarizability in the Hartree,Fock, hybrid-density functional, and density functional modelsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2008Rajendra R. Zope Abstract The sum-over-states (SOS) polarizabilities are calculated within approximate mean-field electron theories such as the Hartree,Fock approximation and density functional models using the eigenvalues and orbitals obtained from the self-consistent solution of the single-particle equations. The SOS polarizabilities are then compared with those calculated using the finite-field (FF) method. Three widely used mean-field models are as follows: (1) the Hartree,Fock (HF) method, (2) the three parameter hybrid generalized gradient approximation (GGA) (B3LYP), and (3) the parameter-free generalized gradient approximation due to Perdew,Burke,Ernzerhof (PBE). The comparison is carried out for polarizabilities of 142 molecules calculated using the 6-311++G(d,p) basis set at the geometries optimized at the B3LYP/6-311G** level. The results show that the SOS method almost always overestimates the FF polarizabilities in the PBE and B3LYP models. This trend is reversed in the HF method. A few exceptions to these trends are found. The mean absolute errors (MAE) in the screened (FF) and unscreened (SOS) polarizability are 0.78, 1.87, and 3.44 Å3 for the HF, B3LYP, and PBE-GGA methods, respectively. Finally, a simple scheme is devised to obtain FF quality polarizability from the SOS polarizability. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Nonempirical calculations of nonlinear optical properties of p -nitroaniline in acetone: Comparison of supermolecule and semicontinuum approachesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2007Marina Yu. Abstract The comparison of the conventional continuum, supermolecule, and semicontinuum models for the description of solvent effect on the (hyper)polarizability of p -nitroaniline (PNA) in acetone is performed. The supermolecule approach is used for the clusters containing PNA and one or two acetone molecules. The account of the specific solute,solvent interactions via the hydrogen bonds formation is shown to result in the enhancement of (hyper)polarizability values. The continuum approach exploited in the framework of polarizable continuum model (PCM) was shown to describe mainly the solvent effect on (hyper)polarizability. The semicontinuum approach, accounting explicitly the interaction between PNA and solvent molecules and treating the rest of the solvent as a continuum, results in a moderate increase of the (hyper)polarizability values compared to those obtained within the conventional PCM approach. All the calculations of (hyper)polarizabilities are performed at the Hartree,Fock level in the aug-cc-pVDZ' Dunning basis set. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Computational linear dependence in molecular electronic structure calculations using universal basis setsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2005D. Moncrieff Abstract Distributed universal even-tempered basis sets have been developed over recent years that are capable of supporting Hartree,Fock energies to an accuracy approaching the sub-,Hartree level. These basis sets have also been exploited in correlation studies, in applications to polyatomic molecules, and in the calculation of electric properties, such as multipole moments, polarizabilities, and hyperpolarizabilities. Jorge and coworkers have also developed universal basis sets and have recently reported applications to diatomic molecular systems. In this article, we compare the molecular calculations reported by Jorge and coworkers with our previous studies. Particular attention is given to the degree of computational linear dependence associated with the various basis sets employed and the consequential effects of the accuracy of the calculated energies. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] A NEMO potential that includes the dipole,quadrupole and quadrupole,quadrupole polarizabilityJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 8 2010Asbjørn Holt Abstract To increase the accuracy of molecular force fields a systematical and balanced improvement of the various terms included is needed. In this work, we have followed this strategy to improve the quality of the NEMO potential for the formaldehyde dimer by introducing local quadrupole moments and higher-order polarizabilities. It is found that inclusion of the quadrupole moment significantly improves the interaction potential. Furthermore, the inclusion of higher-order polarizabilities up to quadrupole,quadrupole polarizability is shown to give a better description of the intermolecular interaction. In addition, it is demonstrated that localized properties based on MP2 densities reproduces the BSSE corrected MP2 interaction energy at large intermolecular separations. This is not the case for HF,SCF based properties. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Revisiting the relationship between the bond length alternation and the first hyperpolarizability with range-separated hybrid functionalsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2008Denis Jacquemin Abstract We monitor the influence of the bond length alternation (BLA) modification on the static electronic polarizability and first hyperpolarizability of two polymethineimine oligomers. Four theoretical approaches are compared: HF, PBE0, LC-,PBE, and MP2. For the dodecamer, both HF and PBE0 are unable to foresee even the qualitative evolution of the first hyperpolarizability when varying the BLA. On the contrary, LC-,PBE provides (non)linear optics properties in agreement with MP2 results, especially for the longer chains. This confirms the interest of range-separated hybrids for the computation of the (hyper)polarizabilities of extended ,-conjugated compounds. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008 [source] Accuracy of distributed multipoles and polarizabilities: Comparison between the LoProp and MpProp modelsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2007P. Söderhjelm Abstract Localized multipole moments up to the fifth moment as well as localized dipole polarizabilities are calculated with the MpProp and the newly developed LoProp methods for a total of 20 molecules, predominantly derived from amino acids. A comparison of electrostatic potentials calculated from the multipole expansion obtained by the two methods with ab initio results shows that both methods reproduce the electrostatic interaction with an elementary charge with a mean absolute error of ,1.5 kJ/mol at contact distance and less than 0.1 kJ/mol at distances 2 Å further out when terms up to the octupole moments are included. The polarizabilities are tested with homogenous electric fields and are found to have similar accuracy. The MpProp method gives better multipole moments unless diffuse basis sets are used, whereas LoProp gives better polarizabilities. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Complete graph conjecture for inner-core electrons: Homogeneous index caseJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 9 2003Lionello Pogliani Abstract The complete graph conjecture that encodes the inner-core electrons of atoms with principal quantum number n , 2 with complete graphs, and especially with odd complete graphs, is discussed. This conjecture is used to derive new values for the molecular connectivity and pseudoconnectivity basis indices of hydrogen-suppressed chemical pseudographs. For atoms with n = 2 the new values derived with this conjecture are coincident with the old ones. The modeling ability of the new homogeneous basis indices, and of the higher-order terms, is tested and compared with previous modeling studies, which are centered on basis indices that are either based on quantum concepts or partially based on this new conjecture for the inner-core electrons. Two similar algorithms have been proposed with this conjecture, and they parallel the two "quantum" algorithms put forward by molecular connectivity for atoms with n > 2. Nine properties of five classes of compounds have been tested: the molecular polarizabilities of a class of organic compounds, the dipole moment, molar refraction, boiling points, ionization energies, and parachor of a series of halomethanes, the lattice enthalpy of metal halides, the rates of hydrogen abstraction of chlorofluorocarbons, and the pED50 of phenylalkylamines. The two tested algorithms based on the odd complete graph conjecture give rise to a highly interesting model of the nine properties, and three of them can even be modeled by the same set of basis indices. Interesting is the role of some basis indices all along the model. © 2003 Wiley Periodicals, Inc. J Comput Chem 9: 1097,1109, 2003 [source] Peak capacity of ion mobility mass spectrometry: the utility of varying drift gas polarizability for the separation of tryptic peptidesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 4 2004Brandon T. Ruotolo Abstract Ion mobility mass spectrometry (IM-MS) peptide mass mapping experiments were performed using a variety of drift gases (He, N2, Ar and CH4). The drift gases studied cover a range of polarizabilities ((0.2,2.6) × 10,24 cm3) and the peak capacities obtained for tryptic peptides in each gas are compared. Although the different gases exhibit similar peak capacities (5430 (Ar) to 7580 (N2)) in some cases separation selectivity presumably based on peptide conformers (or conformer populations), is observed. For example the drift time profiles observed for some tryptic peptide ions from aldolase (rabbit muscle) show a dependence on drift gas. The transmission of high-mass ions (m/z > 2000) is also influenced by increased scattering cross-section of the more massive drift gases. Consequently the practical peak capacity for IM-MS separation cannot be assumed to be solely a function of resolution and the ability of a gas to distribute signals in two-dimensional space; rather, peak capacity estimates must account for the transmission losses experienced for peptide ions as the drift gas mass increases. Copyright © 2004 John Wiley & Sons, Ltd. [source] The relaxations of temporal bond polarizabilities of methylviologen adsorbed on the Ag electrode by 514.5 nm excitation: a Raman intensity studyJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2009Chao Fang Abstract An algorithm to elucidate the temporal bond polarizabilities from the surface enhanced Raman (SERS) intensities was employed to the case of methylviologen (MV) adsorbed on the Ag electrode. This enables us to obtain the properties of its SERS mechanisms and the effect of its adsorption. The analysis shows that the charge transfer and electromagnetic mechanisms involving in this MV SERS system possess different relaxation times for its various temporal bond polarizabilities. The physics is that the process involved in the charge transfer mechanism will take longer time than that involved in the electromagnetic mechanism since it needs more time to redistribute the charges during relaxation. The time division between these two mechanisms is figured out to be around 3 ps for this system. Adsorption also enhances the relaxation of the temporal bond polarizabilities, in general. The adsorption effect is indicated by the temporal bond polarizabilities close to the final stage of relaxation. They are, in fact, the quantities parallel to the bond electronic densities in the molecular orbital (MO) concept. For comparison, the case of MV solid was also analyzed. Copyright © 2008 John Wiley & Sons, Ltd. [source] From Molecule to Bulk Material: Optical Properties of Hydrogen-Bonded Dimers [C12H12N4O2AgPF6]2 and [C28H28N6O3AgPF6]2 Depend on the Arrangement of the Oxime MoietiesCHEMISTRY - A EUROPEAN JOURNAL, Issue 18 2007Wen-Dan Cheng Prof. Abstract The dependence of the optical properties of [C12H12N4O2AgPF6]2 (dimer-1) and [C28H28N6O3AgPF6]2 (dimer-2) on the arrangement of the oxime moieties in the molecule and in bulk crystals was investigated by means of time-dependent density functional theory. Dimer-1 with simple pyridine oxime ligands and a wavy arrangement has a smaller dipole moment and larger transition energy between the two states, and thus smaller third-order polarizabilities and two-photon absorption cross sections. Dimer-2 with extended pyridine oxime ligands and a ladder arrangement has a larger dipole moment and smaller transition energy between the two states, and thus larger third-order polarizabilities and two-photon absorption cross sections. The lowest energy absorption band is red-shifted for dimer-2 as compared with dimer-1, due to more pronounced ,,, delocalization interactions and weaker hydrogen bonding in dimer-2. The electronic absorption spectra, frequency-dependent third-order polarizabilities, and two-photon absorption cross sections involve significant contributions from charge transfers from ,/,* orbitals of the pyridine oxime ligands but no contribution from PF6, ions or H2O molecules in the wavelength range studied for the monomers and dimers of the C12H12N4O2AgPF6 and C28H28N6O3AgPF6 molecules. The third-order susceptibilities and two-photon absorption coefficients of bulk solids were estimated on the basis of the optical properties of the corresponding dimers, and the bulk material constructed from dimer-2 has the larger optical parameters of the two. [source] Multipolar Ordering in Electro- and Magnetostatic Coupled NanosystemsCHEMPHYSCHEM, Issue 9 2008Elena Y. Vedmedenko Dr. habil. Abstract Electric and magnetic multipole moments and polarizabilities are important quantities in studies of intermolecular forces, non-linear optical phenomena, electrostatic, magnetostatic or gravitational potentials and electron scattering. The experimental determination of multipole moments is difficult and therefore the theoretical prediction of these quantities is important. Depending on purposes of the investigation several different definitions of multipole moments and multipole,multipole interactions are used in the literature. Because of this variety of methods it is often difficult to use published results and, therefore, even more new definitions appear. The first goal of this review is to give an overview of mathematical definitions of multipole expansion and relations between different formulations. The second aim is to present a general theoretical description of multipolar ordering on periodic two-dimensional lattices. After a historical introduction in the first part of this manuscript the static multipole expansion in cartesian and spherical coordinates as well as existing coordinate transformations are reviewed. On the basis of the presented mathematical description multipole moments of several symmetric charge distributions are summarized. Next, the established numerical approach for the calculation of multipolar ground states, namely Monte Carlo simulations, are reviewed. Special emphasis is put on the review of ground states in multipolar systems consisting of moments of odd or even order. The last section is devoted to the magnetization reversal in dense packed nanomagnetic arrays, where the magnetic multipole,multipole interactions play an important role. Comparison between the theory and recent experimental results is given. [source] Density Functional Study of Two Seven-Membered Unconventional Fullerenes C58F17CF3 and C58F18CHINESE JOURNAL OF CHEMISTRY, Issue 8 2010Chunmei Tang Abstract The density functional method is used to study the structure, electronic properties, static linear polarizabilities, and optical absorption spectra of two seven-membered unconventional fullerene derivatives C58F17CF3 and C58F18. It is calculated that three sites chosen to locate the CF3 are isoenergetic. The energy gaps of C58F18 and C58F17CF3 are much larger than that of C58, indicating the fluorination and trifluoromethylation of C58 can remarkably enhance the kinetic stability. The density of states explore that the influence of CF3 to the energy levels is mainly distributed in the energy range from ,10 to ,2 eV. However, when the CF3 substitutes for F in C58F18, the bond lengths, energy gaps, static linear polarizabilities, and optical absorption spectra all show small variety. [source] Ab initio prediction of optical rotation: Comparison of density functional theory and Hartree-Fock methods for three 2,7,8-trioxabicyclo[3.2.1]octanesCHIRALITY, Issue 4 2002P.J. Stephens Abstract We report ab initio calculations of the frequency-dependent electric dipole-magnetic dipole polarizabilities, ,(,), at the sodium D line frequency and, thence, of the specific rotations, [,]D, of 2,7,8-trioxabicyclo[3.2.1]octane, 1, and its 1-methyl derivative, 2, using the Density Functional Theory (DFT) and Hartree-Fock/Self-Consistent Field (HF/SCF) methodologies. Gauge-invariant (including) atomic orbitals (GIAOs) are used to ensure origin-independent [,]D values. Using large basis sets which include diffuse functions DFT [,]D values are in good agreement with experimental values (175.8° and 139.2° for (1S,5R)- 1 and - 2, respectively); errors are in the range 25,35°. HF/SCF [,]D values, in contrast, are much less accurate; errors are in the range 75,95°. The use of small basis sets which do not include diffuse functions substantially lowers the accuracy of predicted [,]D values, as does the use of the static limit approximation: ,(,) , ,(o). The use of magnetic-field-independent atomic orbitals, FIAOs, instead of GIAOs, leads to origin-dependent, and therefore nonphysical, [,]D values. We also report DFT calculations of [,]D for the 1-phenyl derivative of 1, 3. DFT calculations find two stable conformations, differing in the orientation of the phenyl group, of very similar energy, and separated by low barriers. Values of [,]D predicted using two different algorithms for averaging over phenyl group orientations are in good agreement with experiment. In principle, the absolute configuration (AC) of a chiral molecule can be assigned by comparison of the optical rotation predicted ab initio to the experimental value. Our results demonstrate the critical importance of the choice of ab initio methodology in obtaining reliable optical rotations and, hence, ACs, and show that, at the present time, DFT constitutes the method of choice. Chirality 14:288,296, 2002. © 2002 Wiley-Liss, Inc. [source] How Do the Different Defect Structures and Element Substitutions Affect the Nonlinear Optical Properties of Lacunary Keggin Polyoxometalates?EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2006A DFT Study Abstract Systematic DFT calculations have been carried out on the lacunary ,-Keggin polyoxometalate derivatives [PW11O39]7,, [XW9O34]n, (X = AlIII, SiIV, GeIV, PV, AsV, and SbV), [XW9M2O39]n,, and [XW9M3O40]n, (X = PV and SiIV, M = MoVI, VV, NbV, and TaV) to investigate the geometric structure and element substitution effects on the molecular nonlinear optical response. Analysis of the computed static second-order polarizability (,0) predicts that the molecular nonlinear optical activity of lacunary Keggin polyoxometalate derivatives can be modified by replacing the central heteroatom and the addenda metal atom. Substitution of the central Al atom or the addenda V atom causes significant enhancement in the molecular nonlinearity. Moreover, the ,0 values are substantially dependent on the defect structures. This class of inorganic complexes possesses remarkably large molecular optical nonlinearity, especially for the partial substitution complex [SiW9Nb2O39]10, (IIIc), which has a computed ,0 value of 2071.0 a.u. Thus, lacunary Keggin polyoxometalates could become excellent candidates in the field of second-order NLO. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Polarizability, Susceptibility, and Dielectric Constant of Nanometer-Scale Molecular Films: A Microscopic ViewADVANCED FUNCTIONAL MATERIALS, Issue 13 2010Amir Natan Abstract The size-dependence of the polarizability, susceptibility, and dielectric constant of nanometer-scale molecular layers is explored theoretically. First-principles calculations based on density functional theory are compared to phenomenological modeling based on polarizable dipolar arrays for a model system of organized monolayers composed of oligophenyl chains. Size trends for all three quantities are primarily governed by a competition between out-of-plane polarization enhancement and in-plane polarization suppression. Molecular packing density is the single most important factor controlling this competition and it strongly affects the bulk limit of the dielectric constant as well as the rate at which it is approached. Finally, the polarization does not reach its "bulk" limit, as determined from the Clausius,Mossotti model, but the susceptibility and dielectric constant do converge to the correct bulk limit. However, whereas the Clausius,Mossotti model describes the dielectric constant well at low lateral densities, finite size effects of the monomer units cause it to be increasingly inaccurate at high lateral densities. [source] Electronic Structure of Self-Assembled Monolayers on Au(111) Surfaces: The Impact of Backbone PolarizabilityADVANCED FUNCTIONAL MATERIALS, Issue 23 2009LinJun Wang Abstract Modifying metal electrodes with self-assembled monolayers (SAMs) has promising applications in organic and molecular electronics. The two key electronic parameters are the modification of the electrode work function because of SAM adsorption and the alignment of the SAM conducting states relative to the metal Fermi level. Through a comprehensive density-functional-theory study on a series of organic thiols self-assembled on Au(111), relationships between the electronic structure of the individual molecules (especially the backbone polarizability and its response to donor/acceptor substitutions) and the properties of the corresponding SAMs are described. The molecular backbone is found to significantly impacts the level alignment; for molecules with small ionization potentials, even Fermi-level pinning is observed. Nevertheless, independent of the backbone, polar head-group substitutions have no effect on the level alignment. For the work-function modification, the larger molecular dipole moments achieved when attaching donor/acceptor substituents to more polarizable backbones are largely compensated by increased depolarization in the SAMs. The main impact of the backbone on the work-function modification thus arises from its influence on the molecular orientation on the surface. This study provides a solid theoretical basis for the fundamental understanding of SAMs and significantly advances the understanding of structure,property relationships needed for the future development of functional organic interfaces. [source] Electric Field-Directed Convective Assembly of Ellipsoidal Colloidal Particles to Create Optically and Mechanically Anisotropic Thin FilmsADVANCED FUNCTIONAL MATERIALS, Issue 20 2009Manish Mittal Abstract A method of simultaneous field- and flow-directed assembly of anisotropic titania (TiO2) nanoparticle films from a colloidal suspension is presented. Titania particles are oriented by an alternating (ac) electric field as they simultaneously advect towards a drying front due to evaporation of the solvent. At high field frequencies (,,>,,25,kHz) and field strengths (E,>,300,V cm,1), the particles orient with their major axis along the field direction. As the front recedes, a uniform film with thicknesses of 1,10,µm is deposited on the substrate. The films exhibit a large birefringence (,n,,,0.15) and high packing fraction (,,=,0.75,±,0.08), due to the orientation of the particles. When the frequency is lowered, the particle orientation undergoes a parallel,random,perpendicular transition with respect to the field direction. The orientation dependence on field frequency and strength is explained by the polarizability of ellipsoidal particles using an interfacial polarization model. Particle orientation in the films also leads to anisotropic mechanical properties, which are manifested in their cracking patterns. In all, it is demonstrated that the field-directed assembly of anisotropic particles provides a powerful means for tailoring nanoparticle film properties in situ during the deposition process. [source] Theoretical studies of some sulphonamides as corrosion inhibitors for mild steel in acidic mediumINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2010Eno E. Ebenso Abstract Density functional theory (DFT) at the B3LYP/6-31G (d,p) and BP86/CEP-31G* basis set levels and ab initio calculations using the RHF/6-31G (d,p) methods were performed on four sulfonamides (namely sulfaacetamide (SAM), sulfapyridine (SPY), sulfamerazine (SMR), and sulfathiazole (STI)) used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies (%IE). The order of inhibition efficiency obtained was SMR > SPY > STI > SAM which corresponded with the order of most of the calculated quantum chemical parameters namely EHOMO (highest occupied molecular orbital energy), ELUMO (lowest unoccupied molecular orbital energy), the energy gap (,E), the Mulliken charges on the C, O, N, S atoms, hardness (,), softness (S), polarizability (,), dipole moment (,), total energy change (,ET), electrophilicity (,), electron affinity (A), ionization potential (I), the absolute electronegativity (,), and the fraction of electrons transferred (,N). Quantitative structure activity relationship (QSAR) approach has been used and a correlation of the composite index of some of the quantum chemical parameters was performed to characterize the inhibition performance of the sulfonamides studied. The results showed that the %IE of the sulfonamides was closely related to some of the quantum chemical parameters but with varying degrees/order. The calculated %IE of the sulfonamides studied was found to be close to their experimental corrosion inhibition efficiencies. The experimental data obtained fits the Langmuir adsorption isotherm. The negative sign of the EHOMO values and other thermodynamic parameters obtained indicates that the data obtained supports physical adsorption mechanism. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Fukui functions for atoms and ions: Polarizability justified approachINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2010Szarek Abstract Recently proposed Fukui function has been tested for a collection of atoms and atomic ions. The key point of the analysis is an approximation for the softness kernel, as an extended and parameterized version of the local approximation s(r,r,) = s(r),(r , r,). The new Fukui functions lead to exact reproduction of global electronic dipole polarizability and atomic softness. The global hardness calculated with the classic definition using new Fukui functions and the hardness kernel |r , r,|,1 matches the , = I , A value with linear correlation superior to any other published hitherto. Applied approximations for the softness and hardness kernels were proved to be in perfect coherence. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Theoretical study on the second-order nonlinear optical properties of nonconjugated D-,-A chromophoresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2009Guochun Yang Abstract Density functional theory calculations have been carried out on nonconjugated D-,-A chromophores to investigate the different electron donors and conjugated bridges effects on the molecular nonlinear optical response. The results show that the large second-order polarizability values can be achieved through careful combination of available electron donors, conjugated bridges for our studied nonconjugated D-,-A chromophores. The calculations also provide a clear explanation for the second-order polarizability changes from the standpoint of transition energies, oscillator strengths, electron density difference, and bond length alternation. Solvent effect has great influence on the second-order polarizability and electronic absorption spectrum. It is hoped that the results presented in this article will give some hints to the interrelated studies. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Comparative study of unscreened and screened molecular static linear polarizability in the Hartree,Fock, hybrid-density functional, and density functional modelsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2008Rajendra R. Zope Abstract The sum-over-states (SOS) polarizabilities are calculated within approximate mean-field electron theories such as the Hartree,Fock approximation and density functional models using the eigenvalues and orbitals obtained from the self-consistent solution of the single-particle equations. The SOS polarizabilities are then compared with those calculated using the finite-field (FF) method. Three widely used mean-field models are as follows: (1) the Hartree,Fock (HF) method, (2) the three parameter hybrid generalized gradient approximation (GGA) (B3LYP), and (3) the parameter-free generalized gradient approximation due to Perdew,Burke,Ernzerhof (PBE). The comparison is carried out for polarizabilities of 142 molecules calculated using the 6-311++G(d,p) basis set at the geometries optimized at the B3LYP/6-311G** level. The results show that the SOS method almost always overestimates the FF polarizabilities in the PBE and B3LYP models. This trend is reversed in the HF method. A few exceptions to these trends are found. The mean absolute errors (MAE) in the screened (FF) and unscreened (SOS) polarizability are 0.78, 1.87, and 3.44 Å3 for the HF, B3LYP, and PBE-GGA methods, respectively. Finally, a simple scheme is devised to obtain FF quality polarizability from the SOS polarizability. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Nonempirical calculations of nonlinear optical properties of p -nitroaniline in acetone: Comparison of supermolecule and semicontinuum approachesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2007Marina Yu. Abstract The comparison of the conventional continuum, supermolecule, and semicontinuum models for the description of solvent effect on the (hyper)polarizability of p -nitroaniline (PNA) in acetone is performed. The supermolecule approach is used for the clusters containing PNA and one or two acetone molecules. The account of the specific solute,solvent interactions via the hydrogen bonds formation is shown to result in the enhancement of (hyper)polarizability values. The continuum approach exploited in the framework of polarizable continuum model (PCM) was shown to describe mainly the solvent effect on (hyper)polarizability. The semicontinuum approach, accounting explicitly the interaction between PNA and solvent molecules and treating the rest of the solvent as a continuum, results in a moderate increase of the (hyper)polarizability values compared to those obtained within the conventional PCM approach. All the calculations of (hyper)polarizabilities are performed at the Hartree,Fock level in the aug-cc-pVDZ' Dunning basis set. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Highly accurate solutions for the confined hydrogen atomINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2007N. Aquino Abstract The model of the confined hydrogen atom (CHA) was developed by Michels et al. 1 in the mid-1930s to study matter subject to extreme pressure. However, since the eigenvalues cannot be obtained analytically, even the most accurate calculations have yielded little more than 10 figure accuracy. In this work, we show that it is possible to obtain the CHA eigenvalues with extremely high accuracy (up to 100 decimal digits) and we do that using two completely different methods. The first is based on formal solution of the confluent hypergeometric function while the second uses a series method. We also compare radial expectation values obtained by both methods and conclude that the wave functions obtained by these two different approaches are of high quality. In addition, we compute the hyperfine splitting constant, magnetic screening constant, polarizability in the Kirkwood approximation, and pressure as a function of the box radius. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Correlated, relativistic, and basis set limit molecular polarizability calculations to evaluate an augmented effective core potential basis setINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 15 2006Nicholas P. Labello Abstract Initial investigations have demonstrated that an augmented ECP basis set can be used to calculate valence electronic properties with deviations of less than 1% from all-electron basis sets. Past work has largely focused on molecules with relatively light atoms (Z<18) examined with time-dependent Hartree,Fock (TDHF) theory. In this work, the dipole moment and polarizability of a number of well-studied molecules are examined with HF, MP2, CCSD, and CCSD(T) correlated wave functions. Additionally, systems not as thoroughly studied due to the difficulty of all-electron calculations when Z=50,85 are included. The SBK ECP basis set, augmented with optimized valence functions, performs well across a broad range of methods, less than 3% different from all electron relativistic and correlated wave functions. Orders of magnitude time savings (101,104) are exchanged for a minimal difference from all-electron basis sets. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] | |||||||||||||||||||||||||||||||