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1.
Avramopoulos A Serrano-Andrés L Li J Reis H Papadopoulos MG 《The Journal of chemical physics》2007,127(21):214102
We employ a series of state-of-the-art computational techniques to study the effect of inserting one or more Xe atoms in HC2H and HC4H, on the linear and nonlinear optical (L&NLO) properties of the resulting compounds. It has been found that the inserted Xe has a great effect on the L&NLO properties of the organoxenon derivatives. We analyze the bonding in HXeC2H, and the change of the electronic structure, which is induced by inserting Xe, in order to rationalize the observed extraordinary L&NLO properties. The derivatives, which are of interest in this work, have been synthesized in a Xe matrix. Thus the effect of the local field (LF), due to the Xe environment, on the properties of HXeC2H, has also been computed. It has been found that the LF effect on some properties is significant. The calculations have been performed by employing a hierarchy of basis sets and the techniques MP2 and CCSD(T) for taking into account correlation. For the interpretation of the results we have employed the complete active space valence bond and CASSCF/CASPT2 methods. 相似文献
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The thermodynamic properties of a fluid of hard spheres with dipole and tetrahedral quadrupole moments are investigated using thermodynamic perturbation theory. The drpole-quadrupole coupling is found to be very important at values of the multipole moments that are close to those of water. 相似文献
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2,3-Bis-(3,4-dicarboxyphenylcarboxyethoxy)-4′-nitrostilbene dianhydride (4) was prepared and reacted with 1,4-phenylenediamine, 4,4′-oxydianiline, 4,4′-diaminobenzanilide and 4,4′-(hexafluoroisopropylidene)dianiline to yield novel polyimides 5-8 containing 2,3-dioxynitrostilbenyl groups as NLO-chromophores, which constituted parts of the polymer backbones. The resulting polyimides 5-8 were soluble in polar solvents such as acetone and DMF. Polymers 5-8 showed a thermal stability up to 300 °C in TGA thermograms with Tg values obtained from DSC thermograms in the range of 135-160 °C. The SHG coefficients (d33) of poled polymer films at the 1064 cm−1 fundamental wavelength were around 5.26 × 10−9 esu. The dipole alignment exhibited exceptionally high thermal stability even at 30 °C higher than Tg and there was no SHG decay below 170-190 °C due to the partial main chain character of polymer structure, which was acceptable for NLO device applications. 相似文献
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Brauer CS Craddock MB Kilian J Grumstrup EM Orilall MC Mo Y Gao J Leopold KR 《The journal of physical chemistry. A》2006,110(33):10025-10034
The Stark effect has been observed in the rotational spectra of several gas-phase amine-hydrogen halide complexes and the following electric dipole moments have been determined: H(3)(15)N-H(35)Cl (4.05865 +/- 0.00095 D), (CH(3))(3)(15)N-H(35)Cl (7.128 +/- 0.012 D), H(3)(15)N-H(79)Br (4.2577 +/- 0.0022 D), and (CH(3))(3)(15)N-H(79)Br (8.397 +/- 0.014 D). Calculations of the binding energies and electric dipole moments for the full set of complexes R(n)()(CH(3))(3)(-)(n)()N-HX (n = 0-3; X = F, Cl, Br) at the MP2/aug-cc-pVDZ level are also reported. The block localized wave function (BLW) energy decomposition method has been used to partition the binding energies into contributions from electrostatic, exchange, distortion, polarization, and charge-transfer terms. Similarly, the calculated dipole moments have been decomposed into distortion, polarization, and charge-transfer components. The complexes studied range from hydrogen-bonded systems to proton-transferred ion pairs, and the total interaction energies vary from 7 to 17 kcal/mol across the series. The individual energy components show a much wider variation than this, but cancellation of terms accounts for the relatively narrow range of net binding energies. For both the hydrogen-bonded complexes and the proton-transferred ion pairs, the electrostatic and exchange terms have magnitudes that increase with the degree of proton transfer but are of opposite sign, leaving most of the net stabilization to arise from polarization and charge transfer. In all of the systems studied, the polarization terms contribute the most to the induced dipole moment, followed by smaller but still significant contributions from charge transfer. A significant contribution to the induced moment of the ion pairs also arises from distortion of the HX monomer. 相似文献
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A.H. Nethercot 《Chemical physics letters》1978,59(2):346-350
As suggested by acharge-transfer model based on Mulliken's definition of electronegativity, the dipole moments of various diatomic molecules and certain photoemission chemical shifts are shown to depend on the normalized electronegativity differences, [(xB ? xA)/], and not simply on (xB ? xA). 相似文献
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Mhuircheartaigh EM Giordani S Blau WJ 《The journal of physical chemistry. B》2006,110(46):23136-23141
We present a study of tetraphenylporphyrin composites formed with single-walled carbon nanotubes (SWNTs). Stable porphyrin/SWNT composite solutions were obtained by non-covalent bonding between the carbon nanotubes and conjugated tetraphenylporphyrin molecules. Transmission electron microscopy reveals porphyrin molecules adhering to the nanotube surface. We report on the first complete linear and nonlinear optical characterization of these nanocomposite materials. The composite solutions were found to be superior optical limiters to nanotubes alone, and to all porphyrin systems studied, including metalloporphyrins. 相似文献
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Lithium rubidium borate (LiRbB4O7) single crystal has been grown by the Czochralski method. Crystalline perfection and optical homogeneity of the grown LiRbB4O7 crystal are analyzed by high resolution X-ray diffraction and birefringence interferometric technique, respectively. Third order nonlinear optical parameters of LiRbB4O7 crystal are determined by Z-scan experimental technique. The nonlinear refractive index (n2) and third-order nonlinear optical susceptibility (χ3) are estimated to be −4.935 × 10−11 cm2/W and 2.719 × 10−7 esu, respectively. The measured (n2) value reveals the self-focusing nature of LiRbB4O7 crystal. 相似文献
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Cisse L Djande A Capo-Chichi M Delatre F Saba A Tine A Aaron JJ 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(3):428-436
The solvent effects on the electronic absorption and fluorescence emission spectra of several coumarins derivatives, containing amino, N,N-dimethyl-amino, N,N-diethyl-amino, hydroxyl, methyl, carboxyl, or halogen substituents at the positions 7, 4, or 3, were investigated in eight solvents with various polarities. The first excited singlet-state dipole moments of these coumarins were determined by various solvatochromic methods, using the theoretical ground-state dipole moments which were calculated by the AM1 method. The first excited singlet-state dipole moment values were obtained by the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga, and Reichardt-Dimroth equations, and were compared to the ground-state dipole moments. In all cases, the dipole moments were found to be higher in the excited singlet-state than in the ground state because of the different electron densities in both states. The red-shifts of the absorption and fluorescence emission bands, observed for most compounds upon increasing the solvent polarity, indicated that the electronic transitions were of π-π* nature. 相似文献
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Molecular dipole moments and polarizabilities, as well as their geometrical derivatives, are given analytical expressions for multiconfiguration self-consistent-field and configuration interaction wavefunctions. By considering the response of the electronic wavefunction induced by electric field and geometrical displacement terms in the Hamiltonian, the response of the total electronic energy to these terms is analyzed. The dipole moment and polarizability are then identified through the factors in the energy which are linear and quadratic in the electric field, respectively. Derivatives with respect to molecular deformation are obtained by identifying factors in these moments which are linear, quadratic, etc., in the distortion parameter. The analytical derivative expressions obtained here are compared to those which arise through finite-difference calculations, and it is shown how previous configuration-interaction-based finite difference dipole moment and polarizability derivatives are wrong. The proper means of treating such derivatives are detailed. 相似文献
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Benavides AL Delgado FJ Gámez F Lago S Garzón B 《The Journal of chemical physics》2011,134(23):234507
New Gibbs ensemble simulation data for a polar fluid modeled by a square-well potential plus dipole-dipole, dipole-quadrupole, and quadrupole-quadrupole interactions are presented. This simulation data is used in order to assess the applicability of the multipolar square-well perturbation theory [A. L. Benavides, Y. Guevara, and F. del Ri?o, Physica A 202, 420 (1994)] to systems where more than one term in the multipole expansion is relevant. It is found that this theory is able to reproduce qualitatively well the vapor-liquid phase diagram for different multipolar moment strengths, corresponding to typical values of real molecules, except in the critical region. Hence, this theory is used to model the behavior of substances with multiple chemical bonds such as carbon monoxide and nitrous oxide and we found that with a suitable choice of the values of the intermolecular parameters, the vapor-liquid equilibrium of these species is adequately estimated. 相似文献
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The triplet state dipole moments mu(T) of a series of 4-amino- and 3-aminobenzonitriles in cyclohexane, benzene, and 1,4-dioxane are recalculated from previously published [J. Phys. Chem. 1992, 96, 10809] time-resolved microwave conductivity data, on the basis of newly measured intersystem crossing yields. For 4-(dimethylamino)benzonitrile (DMABN), the following values are now determined for mu(T): 8.3 D (cyclohexane), 8.9 D (benzene), and 9.7 D (1,4-dioxane), as compared with the previously reported dipole moment of 12 D for the first and the last solvent. With the other aminobenzonitriles, similar mu(T) data are obtained, between 6.9 D for 4-aminobenzonitrile (ABN) in n-hexane and 10.0 D for 4-(di-n-decylamino)benzonitrile (DDABN) in 1,4-dioxane. The increase of mu(T) observed for all aminobenzonitriles when going from cyclohexane via benzene to 1,4-dioxane may indicate that their triplet dipole moments become larger with increasing solvent polarity. The present mu(T) of DMABN, between 8.3 and 9.7 D, although larger than the ground state dipole moment mu(0) of 6.6 D, is somewhat smaller than that of the locally excited (LE) state (9.9 D) but considerably smaller than the dipole moment of the intramolecular charge transfer (ICT) state (17 D). By comparing these mu(X) data with the frequency (CN) of the cyano vibration in each state, it appears that at least for DMABN in the triplet state (CN) is not a reliable indication of the extent of charge transfer as compared with the other states S0, LE, and ICT. 相似文献
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Eleven new ferrocenyl Schiff bases containing a benzene ring and C?N in a conjugating chain have been synthesized by facile methods and characterized by 1H NMR, elemental analysis and fast atom bombardment mass spectrometry. Cyclic voltammetry was used to determine their electrochemical properties and electron‐withdrawing effects. It is shown that these pull–push ferrocenyl compounds have nonlinear optical responses according to their electronic absorption spectra and powder second harmonic generation measurements. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
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采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH (NH2)2)[RE (HCOO)4](RE=Y、Er)。这2种材料是同构的(手性空间群C2221),并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH (NH2)2)[Y (HCOO)4]和(CH (NH2)2)[Er (HCOO)4]分别表现出5.59和5.61 eV的宽光学带隙,对应于222和221 nm的紫外吸收边缘。粉末倍频测量表明,(CH (NH2)2)[Y (HCOO)4]和(CH (NH2)2)[Er (HCOO)4]的倍频效应分别是基准KH2PO4(KDP)的0.32和0.37倍。测量得到(CH (NH2)2)[Y (HCOO)4]和(CH (NH2)2)[Er (HCOO)4]的双折射率分别为0.013和0.015。第一性原理研究表明,2个π共轭的(CH (NH2)2)+和HCOO-基团是光学性质的主要贡献者。 相似文献
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You Jin Cho Hyo Jin No Mi Sung Kim Ju‐Yeon Lee 《Journal of polymer science. Part A, Polymer chemistry》2011,49(8):1784-1790
Novel Y‐type polyester 4 containing 5‐methyl‐4‐{5‐(1,2,2‐tricyanovinyl)‐2‐thiazolylazo}resorcinoxy groups as nonlinear optical (NLO) chromophores, which are parts of the polymer backbone, was prepared, and its NLO properties were investigated. Polyester 4 is soluble in common organic solvents such as N,N‐dimethylformamide and dimethylsulfoxide. Polymer 4 shows a thermal stability up to 250 °C from thermogravimetric analysis with glass‐transition temperature obtained from differential scanning calorimetry of approximately 94 °C. The second harmonic generation (SHG) coefficient (d33) of poled polymer film at 1560‐nm fundamental wavelength is 8.12 × 10?9 esu. The dipole alignment exhibits a thermal stability even at 6 °C higher than glass‐transition temperature (Tg), and no significant SHG decay is observed below 100 °C due to the partial main‐chain character of polymer structure, which is acceptable for NLO device applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献