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The influence of pure solvent and binary solvent mixtures on the optical properties of non-steroidal anti-inflammatory drug (NSAID) molecule, specifically flufenamic acid (FLA), has been studied using absorption and fluorescence spectroscopic techniques. A bathochromic shift is observed in the emission wavelength of FLA with an increase in the solvent polarity of pure solvents, attributed to the highest stability of the excited state. The spectral properties are correlated with Lippert–Mataga, solvent polarity parameter, Kamlet, and Catalan solvent polarity parameters, suggesting that both general and specific solvent effects influence the spectral properties, with general solvent effects dominating over specific solvent effects. Preferential solvation studies have been carried out in tetrahydrofuran (THF) and water solvent mixture, revealing variations in the preference for solvation of FLA as a function of the mole fraction of water. Solvatochromic data are utilized to estimate the excited state dipole moment in pure solvents using different solvatochromic methods, revealing that the excited state dipole moment of FLA is higher than its ground state counterpart. The increase in dipole moment in the excited state compared to the ground state is explained based on intramolecular charge transfer (ICT), with elaboration and discussion on the possible resonance structure corresponding to ICT, inferring the more polar nature of the excited state compared to the ground state. The effect of solute polarizability on the excited state dipole moment and change in dipole moment is also discussed.

Using the effective Lagrangian method, we study the electroweak corrections to the magnetic dipole moment of muon from some special two-loop topological diagrams which are composed of chargino–sneutrino, neutralino–slepton, slepton–sneutrino, in the CP-violating minimal supersymmetric extension of the standard model. Considering the electromagnetic gauge invariance, we obtain the Wilson coefficients of those dimension 6 operators which induce the magnetic dipole moment of leptons. Adopting the zero-momentum substraction scheme, we remove the ultra-violet divergences induced by the divergent sub-diagrams. The numerical results indicate that the two-loop supersymmetric corrections from this sector to the muon magnetic dipole moment can exceed 10^-10, which is the same order of present experimental precision.

First-principles calculations based on Hartree–Fock (HF) and density functional theory (DFT) levels of approximation have been carried out in order to study the stability of graphene clusters as a function of number of carbon atoms (N). The variation of calculated binding energy per carbon atom with corresponding number of carbon atoms (N) in graphene cluster almost saturates after the cluster size consisting of 96 carbon atoms, with binding energy per carbon atom 8.24 eV/atom. Adsorption of halogen atoms, (F, Cl and Br), on hydrogen passivated graphene (H-graphene) was also studied systematically through first-principles DFT calculations by taking five different H-graphene clusters. The calculations showed that the most stable adsorption site for halogen adatoms on H-graphene being T site with binding energy 2.41 eV (F), 1.48 eV (Cl) and 1.19 eV (Br) on the H-graphene cluster consisting 96 carbon atoms. Moreover, on increasing the size of H-graphene cluster, the binding energy of halogen adatoms found to be increasing. The distances of adatom from the nearest carbon atom of H-graphene sheet were 1.47 Å (F), 2.71 Å (Cl) and 3.01 Å (Br), however, the adatom heights from the H-graphene basal plane were 2.22 Å (F), 2.90 Å (Cl), and 3.19 Å (Br). The bonding of halogen adatoms on H-graphene were through the charge transfer; 0.30 |e| (F), 0.37 |e| (Cl) and 0.19 |e| (Br), from H-graphene to adatoms and includes the negligible local distortion in the underlying planner H-graphene. Charge redistribution upon adsorption induces significant dipole moments 2.16 D (F), 4.81 D (Cl) and 3.08 D (Br) on H-graphene. The calculated HOMO–LUMO energy gap of adatom-H-graphene and H-graphene does not differ significantly up to the cluster size N = 30, however, beyond N = 30 adsorption of halogen adatoms significantly opens the HOMO–LUMO energy gap on H-graphene and the opening of HOMO–LUMO energy gap also saturates from N = 96. Correlation of computed HOMO–LUMO energy gap and corresponding binding energy of adatom-H-graphene systems have been also studied.

In this work, we report the results from our spectroscopic study on AlF and AlCl molecules. We carry out detailed electronic structure calculations in both the molecules, including obtaining the potential energy surfaces of the $X^1\mathrm{\Sigma }$ ground electronic state and some of the low-lying excited electronic states belonging to $\mathrm{\Sigma }$ and $\mathrm{\Pi }$ symmetries. This is followed by evaluating the spectroscopic constants and molecular properties such as electric dipole moments and electric quadrupole moments. Throughout, we employ the multi-reference configuration interaction method and work with high-quality quadruple zeta basis sets. Further, transition dipole moments between the ground electronic state and singlet excited states are also studied. The relevant vibrational parameters are computed by solving the vibrational Schrödinger equation. Subsequently, the vibrational energy spacings and transition dipole moments between the vibrational levels belonging to the same electronic states are used to evaluate the spontaneous and black-body radiation-induced transition rates, followed by computing the lifetimes. Finally, the energy differences between rotational levels belonging to different vibrational levels and within an electronic state as well as the Einstein coefficients are reported.

Viscosities (η, N s m^-2) and surface tensions (γ, N m^-1) of methanol, ethanol, glycerol, ethyl acetate, n-hexane, diethyl ether, chloroform, benzene, carbon tetrachloride (CCl₄), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, and formic acid have been measured with survismeter and compared with the data obtained by Ubbehold viscometer and stalagmometer, respectively. The ±1.1 × 10^-5N s m^-2 and ±1.3 × 10^-6N m^-1 deviations are noted in the data, in fact literature data of surface tension and viscosity are available to 2nd and 3rd place of decimals, respectively, while the survismeter measures them to 3rd and 4th place of decimals, respectively. The survismeter is 2-in-1 for viscosity and surface tension measurements together with high accuracies several times better than those of the separately measured data. Viscosities and surface tensions of aqueous DMSO, THF, DMF, and acetonitrile from 0.01 to 0.20 mol kg^-1 and mannitol from 0.005 to 0.02 mol kg^-1 have been measured with survismeter with ±1.2 × 10^-5N s m^-2 and ±1.3 × 10^-6N m^-1 deviations, respectively. The data are used for friccohesity and dipole moment determination, the lower viscosities, surface tension, and friccohesity values are noted for mannitol as compared to DMSO, THF, DMF, and acetonitrile solutions. The weaker molecular interactions are noted for mannitol. As compared to viscometer and stalagmometer individually, it is inexpensive and minimizes 2/3rd of consumables, human efforts, and infrastructure with 10 times better accuracies.

Monodispersed DAST nanocrystals have almost been successfully fabricated by means of the inverse reprecipitation method. By employing AC electric field, high electric field of above ca. 1.0 kVcm^-1 could be applied to polar DAST nanocrystals dispersed in decahydronaphthalene, so as to avoid electrophoresis of nanocrystals under DC electric field. The response of DAST nanocrystal dispersion to applied AC electric field was analyzed phenomenologically by fitting Langevin function, which provided a large permanent dipole moment of DAST nanocrystal. In addition, we have succeeded in in situ observation of AC electric-field-induced orientational motion of DAST crystals by using an optical microscope. The present DAST nanocrystal dispersion system will be expected as an optical device like display monitor.

This paper presents dipole moments, static isotropic polarizabilities and polarizability anisotropies of 20 molecules calculated in the framework of a new natural orbital functional method. All calculations have been performed using a finite field approach. Comparison with other correlated methods (CCSD(T), B3LYP) shows a reasonable agreement in the prediction of electric response properties by this new functional.

In the present work, the new formulations describing spectral shifts by the authors have been introduced and employed to investigate two dye molecules, 6-propanoyl-2-(N,N-dimethylamino) naphthalene and 4-(N,N-dimethylamino) benzonitrile. From the viewpoints of the authors, the cavity radii were overestimated owing to the errors existing in the traditional models. Slightly differing from the results by other authors in the past, this work fits the cavity radii to the values of ~4.5 Å for 6-propanoyl-2-(N,N-dimethylamino) naphthalene and ~3.2 Å for 4-(N,N-dimethylamino) benzonitrile. In the fittings, both point dipole approximation and multipole expansion methods are employed. The calculations of the excited states are performed by means of the time-dependent density functional theory. Comparing the fitted cavity radii from the experimental spectra with those estimated from the molecular volumes by some well-known procedures such as COSMO and PCM, we find that the new formulations give fairly satisfactory results. By taking an atomic ion as an example, the authors argue that the Onsager radii recommended by some popular procedures are greatly exaggerated. The cavity radius derived simply from the volume encompassed by the solvent-accessible surface, without any addition of other parts, is suggested for application.

A simple expression for the distance between two electrons, (δr₁₂)_ab, has been defined from one-electron expectation values. This value is calculated for triplet and singlet systems of two electrons, and closed-shell molecules of up to 58 electrons. When (δr₁₂)_ab is compared to the corresponding coulomb integral, J_ab, an interesting relationship is observed. The relationship is followed extremely closely by all pairs of electrons, except for some deviations involving delocalized core–core electron pairs.

Theoretical insight into the mechanism of C8 adducts formation in a series of complicated carcinogenic reactions has been provided in a previous work. However, two important issues involved in this mechanism still need to be elucidated in detail. Hence, in this paper, we first present a new theoretical model to study the direct formation mechanism of C8 adduct. It is found that this model can well reflect the actual interactions in the real carcinogenic reactions. Thus, a better theoretical model to simulate other properties of these complicated reactions is found using ab initio and density functional theory (DFT) methods. Second, we simulate the formation process of C8 adduct in this new theoretical model using ABEEM/MM-MD method. According to the MD study, we approve that the higher aqueous-phase activation energy for transition state in this kind of reaction contributes to weaker interactions between central sites of reaction and water compared with those for reactants. This study once more supports the mechanism of formation of C8 adducts in the actual carcinogenic reactions where arylnitrenium ions directly attack at C8 positions of nucleoside bases in DNA.

The electronic properties, polarizabilities, first and second hyperpolarizabilities of YO_n clusters of $n=1$–12 were studied using the quantum chemical method. The vertical ionization potential (VIP) values for the anionic clusters increase monotonically with the cluster size. Among the neutral clusters YO₃ and YO₈ have the least chemical hardness values, where in anionic clusters with size $n<4$ possesses the least chemical hardness. Anionic clusters have more electrons attracting tendency than the neutral clusters. The computed static mean polarizability of neutral yttrium oxides has positive values but is close to zero. The incorporation of oxygen atom quenches the polarizability of yttrium. The computed polarizability anisotropy of neutral clusters shows an oscillatory effect both at static and at dynamic conditions. The first hyperpolarizability for many YO_n clusters are close to zero. The existence of high symmetry in these clusters reduces the first hyperpolarizability values which was supported by the small dipole moments. The computed $\gamma$ values for the static neutral and anionic clusters show only a small variation. The decrease in the polarizability and second hyperpolarizability with size can be interpreted in terms of the electronic delocalization and chemical bonding in the clusters.

In the present investigation, for the first time, we have performed a thorough study about different functionals and basis sets for linear and nonlinear optical (NLO) properties of para-nitroaniline ($p$-NA), which is considered as proto-type NLO molecule, among organic NLO materials. There is a dire need of such data base for $p$-NA because many investigators are using such values of $p$-NA for comparative analysis. A range of different functionals including HF, BLYP, PW91, PBE, B3LYP, M06, M06-2X, PBE0, BHandHLYP, CAM-B3LYP, LC-BLYP, and B3LYP-D3 are applied in conjugation with several commonly basis sets such as 6-31G*, 6-311G*, 6-311G**, 6-311+G**, cc-pVDZ, and cc-pVTZ. A variety of functional and basis sets combinations are calculated and graphically compared with each other. The calculated total dipole moment for the $p$-NA is found to be 6.79D which is quite closer to experimentally determined value. The lowest calculated value for linear isotropic polarizability at HF/6-31G* level of theory is $11.74\times 10^{-24}$ esu while higher values observed with remaining all methods especially 14% polarizability increases in presence of basis set with diffuse functions and similar trend of variation is also observed in linear anisotropic polarizability. Similarly, the calculated value of frequency dependent second-order polarizability is found to be $9.59\times 10^{-30}$ esu at PBE0/6-311+G** level of theory which is quite closer to experimental value of $9.6\times 10^{-30}$ esu. A comparison between the calculated and experimental results shows good agreement among geometries, dipole moments and NLO polarizabilities for $p$-NA. Moreover, the frontier molecular orbital (FMO) and electron density difference map (EDDM) analysis along with density of state (DOS) plots are also presented to get more physical intuitions into the structure–property relationship and electronic communications between terminal accepter and donor groups through $\pi$-conjugation. The present investigation provides benchmark data including various commonly used functionals and basis sets for the calculation of NLO properties of $p$-NA. Thus, the present investigation will put straight several future studies when it comes to comparative NLO study of organic materials.

Introduction of functional groups on a $\pi$-conjugated system is one of the most promissing methods to modulate their chemical and physical properties. Here, dinitrohexapyrrolohexaazacoronene (dinitroHPHAC) was synthesized, in which two nitro groups are introduced at the same pyrrole ring. The dinitroHPHAC possesses a large dipole moment ($\mu$ = 11.7 D at B3LYP/6-31G(d,p)) and showed solvatochromism with decreased HOMO-LUMO energy gap. Interestingly, the colour of the solid is black to the naked eye. The global aromaticity of the dication state is decreased compared with those of pristine HPHAC and mononitroHPHAC.

The dependence of the parameters of the capacitance effect in heterogeneous dispersed two-component structures based on semiconductors from the bulk fraction of the semiconductor component is modeled. The used method for determining the changes of the energy bands bending on the surface of the spherical semiconductor particle by applying dc electric field allowed to calculate the changes of the dipole moment and effective (taking into account the polarization of the free charge) dielectric constant of this semiconductor particle. This result allowed to use the known models of the dielectric constant of two-component structures for the description of the capacitance field effect in the heterogeneous structures. The relations allowing to estimate the value of the bulk donor concentration in the semiconductor component of the matrix of the heterogeneous system and the statistical mixture have been obtained. The approbation of the obtained calculation relations to evaluate the donor concentration in the ZnO grains of zinc oxide varistor ceramics leads to the correct values that are consistent with estimates of other methods and models. It is established that the sensitivity of the relative dielectric constant to the applied dc electric field is dependent on the bulk fraction of the semiconductor particles in the heterogeneous structures. The bulk fraction of the semiconductor particles significantly affects on the dielectric constant beginning with the values from $\sim 0.8$ for matrix systems and $\sim 0.33$ for statistical mixtures.

Molecular dynamics (MD) simulations play a crucial role in modeling biomolecular systems in which the electrostatic interactions are critical in dictating the structural and dynamical properties. Thus, the treatment of the electrostatic interactions defined in the underlying force field (FF) strongly affects the simulation accuracy. Most FFs use fixed partial atomic charges to include electrostatic interactions, and therefore lack the electronic polarization response, representing an intrinsic limitation. To address this limitation, polarizable FFs have been developed that treat atomic polarizabilities explicitly. Here we present the application of the all-atom polarizable (Drude) and non-polarizable (CHARMM) nucleic acid FFs in RNA hairpin systems to investigate the impact of polarization on structural properties, dipole moment distributions, and cation interactions. Results show that the presence of polarizability in the FF significantly improves the stabilization of RNA hairpin structure. As expected, the distributions of dipole moments show more fluctuations when simulated using the polarizable FF, with the variation in dipoles contributing to the stabilization of the structures of the loop regions of the RNAs. Contact map analyses between the bases and cations show that the variation of the ion distribution around the entire hairpin is larger for the polarizable FF and the cations occupy the outer hydration shell to a greater extent. The presented results indicate the importance of the explicit treatment of electronic polarizability in molecular simulations of RNA, including in non-canonical regions.

With the gas ionization experiments (Section 1.7) we know that atoms and molecules are made of nuclei and electrons that revolve around them. In this chapter we give representations of these microscopic objects and show how certain atoms or molecular fragments form bonds between them. From the description of the hydrogen atom, the lightest atom in Nature since it contains only one proton and one electron, we will develop a simple model for the bonds between atoms in molecules stable at 25°C. Without making complicated calculations we will be able to predict which bonds between atoms are possible a priori and which structures the molecules containing them have. Atoms are the parts of a Lego® set that can be assembled to make a large number of constructions, but not just any construction (three-dimensional objects with predefined geometries). In Chapter 7, we will develop a slightly more advanced model of the chemical bond. We will examine why some bonds are weaker than others, i.e. which bonds are more or less easily broken by heating…

The stability of an organic compound depends on its nature and the environment in which it is placed. It depends on the presence or absence of reagents (acid, base, oxidizing agent, reducing agent, light, etc.) and catalysts. The stability may not be the same in the solid, liquid or gaseous state. In a homogenous solution, the stability might be affected by the polarity of the solvent and its concentration. For instance a polar solvent favors ionization. In a non-polar solvent ionization is difficult. In the gas phase ionization never occurs. In the gas phase and in solution stability depends on pressure and the presence of impurities. We are interested here in the thermal stability of pure compounds in the gas phase or in non-polar solvents under one atmosphere…

Monodispersed DAST nanocrystals have almost been successfully fabricated by means of the inverse reprecipitation method. By employing AC electric field, high electric field of above ca. 1.0 kVcm^-1 could be applied to polar DAST nanocrystals dispersed in decahydronaphthalene, so as to avoid electrophoresis of nanocrystals under DC electric field. The response of DAST nanocrystal dispersion to applied AC electric field was analyzed phenomenologically by fitting Langevin function, which provided a large permanent dipole moment of DAST nanocrystal. In addition, we have succeeded in in situ observation of AC electric-field-induced orientational motion of DAST crystals by using an optical microscope. The present DAST nanocrystal dispersion system will be expected as an optical device like display monitor.

The structure, packing, and charge distribution in molecules of nonlinear optical materials have been analysed with reference to their counterparts in centrosymmetric structures based on low temperature X-ray measurements. The systems studied are the centric and noncentric polymorphs of 5-nitrouracil as well as the diamino, dithio, and thioamino derivatives of 1,1-ethylenedicarbonitrile; the latter possesses a noncentric structure. The molecular structure of 5-nitrouracil is invariant between the two forms, while the crystal packing is considerably different, leading to dimeric N–H⋯O rings in the centric polymorph and linear chains in noncentric one. There is an additional C–H⋯O contact in the centric form with a significant overlap of the electrostatic potentials between the alkenyl hydrogen atom and an oxygen atom of the nitro group. The dipole moment of 5-nitrouracil in the noncentric form is much higher (μ=9 D) than in the centric form (≈6 D). Among the 1,1-ethylenedicarbonitriles, there is an increased charge separation in the noncentric thioamino derivative, leading to an enhanced dipole of 15 D compared to the centric diamino (5 D) and dithio (6 D) derivatives. The effect of the crystal field is borne out by semiempirical AM1 calculations on the two systems. Dipole moments calculated for the molecules in the frozen geometries match closely with those abtained fro centric crystals from the experimental charge densities. The calculated values of the dipole moment in the frozen or optimized geometries in the noncentric structures are, however, considerably lower than the observed value. Furthermore, the conformation of the S–CH₃, group in the noncentric crystal is anti with respect to the central C=C bond while the syn conformation is anti with respect to the central C=C bond while the syn conformation is predicted for the free molecule in the optimized geometry.

Molecular dynamics (MD) simulations play a crucial role in modeling biomolecular systems in which the electrostatic interactions are critical in dictating the structural and dynamical properties. Thus, the treatment of the electrostatic interactions defined in the underlying force field (FF) strongly affects the simulation accuracy. Most FFs use fixed partial atomic charges to include electrostatic interactions, and therefore lack the electronic polarization response, representing an intrinsic limitation. To address this limitation, polarizable FFs have been developed that treat atomic polarizabilities explicitly. Here we present the application of the allatom polarizable (Drude) and non-polarizable (CHARMM) nucleic acid FFs in RNA hairpin systems to investigate the impact of polarization on structural properties, dipole moment distributions, and cation interactions. Results show that the presence of polarizability in the FF significantly improves the stabilization of RNA hairpin structure. As expected, the distributions of dipole moments show more fluctuations when simulated using the polarizable FF, with the variation in dipoles contributing to the stabilization of the structures of the loop regions of the RNAs. Contact map analyses between the bases and cations show that the variation of the ion distribution around the entire hairpin is larger for the polarizable FF and the cations occupy the outer hydration shell to a greater extent. The presented results indicate the importance of the explicit treatment of electronic polarizability in molecular simulations of RNA, including in non-canonical regions.