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Molecular Orbital Calculations (molecular + orbital_calculation)
Kinds of Molecular Orbital Calculations Selected AbstractsInfluence of substituents on the kinetics of epoxy/aromatic diamine resin systemsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2004Heping Liu Abstract Eleven different epoxy/diamine systems, including tetraglycidyl-4,4,-diaminodiphenylmethane (TGDDM), triglycidyl p -aminophenol (TGAP), and diglycidyl ether of bisphenol A (DGEBA) with 4,4,-diaminodiphenylsulfone (DDS), diethyltoluenediamine (DETDA), dimethylthiotoluenediamine (DMTDA), and meta -phenylenediamine (m -PDA), were studied with near-infrared spectroscopy at different temperatures. The reactivities of the epoxies were determined and found to be in the following order when reacted with the same amine: DGEBA > TGAP > TGDDM. When the primary amine was reacted with the same epoxy, the order was DETDA > DDS > DMTDA; for the secondary amine, the order was DETDA > DMTDA > DDS. The relative reaction rates of the secondary amine to the primary amine were compared and discussed in terms of the structural differences and the corresponding substitution effect. It was concluded that the increase in the secondary amine reactivity of DETDA and DMTDA was caused by the deconjugation of the benzene-ring , electrons from the lone pair on the N atom. The overall order of the secondary amine relative reactivity was DMTDA > DETDA > DDS for the same epoxy and TGDDM > TGAP > DGEBA for the same amine. The m -PDA systems had no significant positive or negative substitution effects. Molecular orbital calculations were performed, and the results showed the most significant deconjugation effect in the secondary amine of DETDA. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3143,3156, 2004 [source] Deformed Phthalocyanines: Synthesis and Characterization of Zinc Phthalocyanines Bearing Phenyl Substituents at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-PositionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 18 2005Takamitsu Fukuda Dr. Abstract The synthesis of a series of zinc phthalocyanines partially phenyl-substituted at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-positions (the so-called ,-positions) is reported. Macrocycle formation based on 3,6-diphenylphthalonitrile, o -phthalonitrile, and zinc acetate predominantly yielded the near-planar disubstituted complex and opposite tetrasubstituted isomer, while the lithium method yielded the sterically hindered hexasubstituted complex and adjacent tetrasubstituted isomer. All compounds have been characterized by 1H NMR, MALDI-TOF-MS, and elemental analysis methods. In addition, crystal structures have been solved for the di-, hexa-, and octasubstituted complexes and the adjacent tetrasubstituted isomer. DFT geometry optimization calculations predict more highly deformed structures than those observed in the crystals. The packing force of the crystals cannot therefore be ignored, particularly for the less phenyl-substituted derivatives. The crystal structures have revealed that overlap of the phenyl groups causes substantial deformation of the phthalocyanine (Pc) ligands within the crystals, while strong ,,, stacking in the remainder of the Pc moiety lacking phenyl substituents can suppress the impact of the deformation. Absorption spectra show sizable red shifts of the Q-band with increasing number of phenyl groups. Analysis of the results of absorption spectra and electrochemical measurements reveals that a substantial portion of the red shift is attributable to the ring deformations. Molecular orbital calculations lend further support to this conclusion. A moderately intense absorption band emerging at around 430 nm for highly deformed octaphenyl-substituted zinc Pc can be assigned to the HOMO,LUMO+3 transition, which is parity-forbidden for planar Pcs, but becomes allowed since the ring deformations remove the center of symmetry. [source] Electronic and Vibrational Properties of Fluorenone in the Channels of Zeolite LCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2004André Devaux Dr. Abstract Fluorenone (C13H8O) was inserted into the channels of zeolite L by using gas-phase adsorption. The size, structure, and stability of fluorenone are well suited for studying host,guest interactions. The Fourier transform IR, Raman, luminescence, and excitation spectra, in addition to thermal analysis data, of fluorenone in solution and fluorenone/zeolite L are reported. Normal coordinate analysis of fluorenone was performed, based on which IR and Raman bands were assigned, and an experimental force field was determined. The vibrational spectra can be used for nondestructive quantitative analysis by comparing a characteristic dye band with a zeolite band that has been chosen as the internal standard. Molecular orbital calculations were performed to gain a better understanding of the electronic structure of the system and to support the interpretation of the electronic absorption and luminescence spectra. Fluorenone shows unusual luminescence behavior in that it emits from two states. The relative intensity of these two bands depends strongly on the environment and changes unexpectedly in response to temperature. In fluorenone/zeolite L, the intensity of the 300 nm band (lifetime 9 ,s) increases with decreasing temperature, while the opposite is true for the 400 nm band (lifetime 115 ,s). A model of the host,guest interaction is derived from the experimental results and calculations: the dye molecule sits close to the channel walls with the carbonyl group pointing to an Al3+ site of the zeolite framework. A secondary interaction was observed between the fluorenone's aromatic ring and the zeolite's charge-compensating cations. [source] Unified quantum molecular dynamics method based on centroid molecular dynamics and semiempirical molecular orbital theoryINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2003Yasuhito Ohta Abstract We have developed a unified quantum molecular dynamics method, in which the centroid molecular dynamics including the quantum effect of atomic nuclei is unified with the semiempirical molecular orbital calculation for the atomic configuration generated in the molecular dynamics. This unified method has successfully been applied to a couple of diatomic molecular systems for examining its performance. The method has yielded excellent agreement with exact quantum results and taken sufficiently short CPU time for practical use. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 [source] Metastable ion study of organosilicon compounds.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 7 2001(CH3)2Si(OCH3), CH3SiH(OCH3), Part XIII: dimethoxydimethylsilane, dimethoxymethylsilane Abstract Unimolecular metastable fragmentations of dimethoxydimethylsilane, (CH3)2Si(OCH3)2 (MW 120, 1), and dimethoxymethylsilane, CH3SiH(OCH3)2 (MW 106, 2), upon electron impact ionization have been studied by means of mass-analyzed ion kinetic energy (MIKE) spectrometry and the D-labeling technique in conjunction with thermochemistry. The results have been compared with those of the corresponding carbon analogues, 2,2-dimethoxypropane, (CH3)2C(OCH3)2 (MW 104, 3) and 1,1-dimethoxyethane, CH3CH(OCH3)2 (MW 90, 4). In analogy with the cases of 3 and 4, both molecular ions from 1 and 2 are formed at very low abundance at 70 eV, and begin to decompose by the expulsion of the substituents (H, CH3 or OCH3) on the central silicon atom. These decompositions are followed by the loss of a formaldehyde molecule (CH2O), as commonly observed in the mass spectra of methoxysilanes. Further, an ethylene (C2H4) or a dimethyl ether (CH3OCH3) molecule loss is observed in the fragmentation of some intermediate ions generated from 1+· and 2+·, but the mechanisms are different than those in the cases of 3 and 4. Some of these fragmentations are also different than those reported previously. The relative abundance of the ions in many MIKE spectra is explained by the extension of the Stevenson,Audier rule. The reaction, which is in contrast to the rule, however, is rationalized by the energy of the transition state for the reaction, estimated by semi-empirical molecular orbital calculation. The peak at m/z 59 from 2+· consists only of CH3OSi+ ion, whereas the peak from 1+· consists of two different ions, CH3OSi+ and (CH3)2Si+H. The ions CH3OSi+ from 1+· and 2+· are generated by at least two and three separate routes respectively. Copyright © 2001 John Wiley & Sons, Ltd. [source] The local structure of ,-FeSi2 under high pressurePHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 3 2009Yoshihisa Mori Abstract We report the results of the high-pressure X-ray diffraction study and the high-pressure extended X-ray absorption fine structure study for ,-FeSi2 using the synchrotron radiation sources. The bond lengths of Fe,Fe, Si,Si, and Fe,Si under pressure were refined by the Rietveld method and the EXAFS analysis. It is interesting that the bond length of Si,Si is almost unchanged with increasing pressure. The DV-X, molecular orbital calculation was carried out for the crystal structure at 34.9 GPa and shows that the highest occupied molecular orbital consists of only 3d orbital of Fe atom. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Crystal structure of achiral nonapeptide Boc,(Aib,,zPhe)4,Aib,OMe at atomic resolution: Evidence for a 310 -helixBIOPOLYMERS, Issue 3 2003Yoshihito Inai Abstract An x-ray crystallographic analysis was carried out for Boc,(Aib,,ZPhe)4,Aib,OMe (1: Boc = t -butoxycarbonyl; Aib = ,-aminoisobutyric acid; ,ZPhe = Z -,,,-didehydrophenylalanine) to provide the precise conformational parameters of the octapeptide segment ,(Aib,,ZPhe)4,. Peptide 1 adopted a typical 310 -helical conformation characterized by ,,, = ±55.8° (50°,65°), ,,, = ±26.7° (15°,45°), and ,,, = ±179.5° (168°,188°) for the average values of the ,(Aib,,ZPhe)4, segment (the range of the eight values). The 310 -helix contains 3.1 residues per turn, being close to the "perfect 310 -helix" characterized by 3.0 residues per turn. NMR and Fourier transform infrared (FTIR) spectroscopy revealed that the 310 -helical conformation at the atomic resolution is essentially maintained in solution. Energy minimization of peptide 1 by semiempirical molecular orbital calculation converged to a 310 -helical conformation similar to the x-ray crystallographic 310 -helix. The preference for a 310 -helix in the ,(Aib,,ZPhe)4, segment is ascribed to strong inducers of the 310 -helix inherent in Aib and ,ZPhe residues,in particular, the Aib residues tend to stabilize a 310 -helix more effectively. Therefore, the ,(Aib,,ZPhe)4, segment is useful to rationally design an optically inactive 310 -helical backbone, which will be of great importance to provide novel insights into noncovalent and covalent chiral interactions of a helical peptide with a chiral molecule. © 2003 Wiley Periodicals, Inc. Biopolymers 70: 310,322, 2003 [source] Sodiated ,-Diphosphonate Carbanions: Characterization of the Tetrameric Cubane and the Hexameric Ladder Complexes [{(iPrO)2P(O)}2CHNa]4 and [{(EtO)2P(O)}2CHNa]6EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2003Roger Nassar Abstract Reaction of the methylene diphosphonates [(RO)2P(O)]2CH2, where R = iPr or Et, with the metalating reagents NaH, nBuNa or the superbasic mixture tBuONa/nBuLi leads to monodeprotonation, and formation of the complexes [{(iPrO)2P(O)}2CHNa]4 (1) and [{(EtO)2P(O)}2CHNa]6 (2). Single-crystal X-ray diffraction studies revealed that 1 is tetrameric in the solid state, with a central Na4O4 cubane core. Each metal in 1 is rendered pentacoordinate by binding to three ,3 -O phosphoryl bridges within the cubane, a chelating phosphoryl unit, and also a single iPrO group. In contrast, the structure of 2 is hexameric, and is composed of an unusual six-rung Na6O6 ladder core. Three distinct sodium environments as well as ,1 -, ,2 - and ,3 -O phosphoryl units are present within the ladder framework. No Na,C interactions are present in either 1 or 2. All of the six-membered NaOPCPO chelate rings display localized P=O double bonds and partial multiple bonding on the P,C,P linkages (mean P,O: 1.49 Å, and mean P,C: 1.69 Å). Ab initio molecular orbital calculations (HF/6,31G*) on model complexes indicate that the hexameric arrangement found for 2 is thermodynamically more stable than the cubane structure of 1, in the absence of steric effects. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Dye-Sensitized Solar Cells Based on a Novel Fluorescent Dye with a Pyridine Ring and a Pyridinium Dye with the Pyridinium Ring Forming Strong Interactions with Nanocrystalline TiO2 FilmsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 1 2010Yousuke Ooyama Abstract As new-type donor,acceptor ,-conjugated dyes capable of forming a strong interaction between the electron-acceptor moiety of the sensitizers and a TiO2 surface, fluorescent dye OH11 and pyridinum dye OH12 with a pyridine and pyridinium ring as the electron-accepting group, respectively, have been designed and synthesized as photosensitizers for use in dye-sensitized solar cells (DSSCs). The fluorescent dye OH11 exhibits an absorption band at around 410 nm and a fluorescence band at around 530 nm. On the other hand, the pyridinum dye OH12 shows an absorption maximum at around 560 nm, assigned to a strong intramolecular charge-transfer excitation from the dibutylamino group to the pyridinium ring. The short-circuit photocurrent densities of the DSSCs prepared by using OH11 and OH12 are 4.33 and 1.74mA cm,2, and the solar energy-to-electricity conversion yields are 1.33 and 0.51,%, respectively, under simulated solar light [AM (air mass) 1.5, 100 mW,cm,2]. The open-circuit photovoltage for OH11 (525 mV) is higher than that of OH12 (444 mV). The effects of the configuration of the dyes on the TiO2 surface and of their chemical structures on the photovoltaic performances are discussed on the basis of semi-empirical molecular orbital calculations (AM1 and INDO/S), spectral analyses and cyclic voltammetry. [source] Theoretical study of acetonitrile-exchange reactions on hexasolvated divalent cations in the first transition series elementsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 10 2009Hiroaki Wasada Abstract Penta-, hexa-, and heptaacetonitrile complexes of divalent cations of the first transition series are studied by ab initio molecular orbital calculations. The factors that determine the structural stability and the reaction mechanism of solvent-exchange reactions are discussed. All the penta- and hexaacetonitrile species are at local minima, whereas the geometrical stability of the heptacoordinated species depends on the 3d electron configurations. The structural stability of heptaacetonitrile species is intermediate between those of hydrogen cyanide complexes and hydrates. Acetonitrile exchange reactions have more dissociative character than hydrogen cyanide exchange reactions because the inductive effect of the methyl group in CH3CN destabilizes the heptacoordinated structures. The successive binding energies show that associative mechanisms are favorable for acetonitrile exchange with earlier members of the first transition series, whereas dissociative mechanisms become favorable for later members. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Implementation of divide-and-conquer method including Hartree-Fock exchange interactionJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2007Tomoko Akama Abstract The divide-and-conquer (DC) method, which is one of the linear-scaling methods avoiding explicit diagonalization of the Fock matrix, has been applied mainly to pure density functional theory (DFT) or semiempirical molecular orbital calculations so far. The present study applies the DC method to such calculations including the Hartree-Fock (HF) exchange terms as the HF and hybrid HF/DFT. Reliability of the DC-HF and DC-hybrid HF/DFT is found to be strongly dependent on the cut-off radius, which defines the localization region in the DC formalism. This dependence on the cut-off radius is assessed from various points of view: that is, total energy, energy components, local energies, and density of states. Additionally, to accelerate the self-consistent field convergence in DC calculations, a new convergence technique is proposed. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Development of polyphosphate parameters for use with the AMBER force fieldJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 9 2003Kristin L. Meagher Abstract Accurate force fields are essential for reproducing the conformational and dynamic behavior of condensed-phase systems. The popular AMBER force field has parameters for monophosphates, but they do not extend well to polyphorylated molecules such as ADP and ATP. This work presents parameters for the partial charges, atom types, bond angles, and torsions in simple polyphosphorylated compounds. The parameters are based on molecular orbital calculations of methyldiphosphate and methyltriphosphate at the RHF/6-31+G* level. The new parameters were fit to the entire potential energy surface (not just minima) with an RMSD of 0.62 kcal/mol. This is exceptional agreement and a significant improvement over the current parameters that produce a potential surface with an RMSD of 7.8 kcal/mol to that of the ab initio calculations. Testing has shown that the parameters are transferable and capable of reproducing the gas-phase conformations of inorganic diphosphate and triphosphate. Also, the parameters are an improvement over existing parameters in the condensed phase as shown by minimizations of ATP bound in several proteins. These parameters are intended for use with the existing AMBER 94/99 force field, and they will permit users to apply AMBER to a wider variety of important enzymatic systems. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1016,1025, 2003 [source] Hydrogen storage properties of B- and N-doped microporous carbonAICHE JOURNAL, Issue 7 2009Lifeng Wang Abstract A B- and N-doped microporous carbon has been synthesized via a substitution reaction. The obtained carbon exhibited much higher surface area than the previously reported B- and N-doped carbon. The hydrogen storage measurements indicated that the B- and N-doped microporous carbon had a 53% higher storage capacity than the carbon materials with similar surface areas. Furthermore, hydrogen storage via spillover was studied on Ru-supported B- and N-doped microporous carbon and a storage capacity of 1.2 wt % at 298 K and 10 MPa was obtained, showing an enhancement factor of 2.2. Ab initio molecular orbital calculations were also performed for the binding energies between the spiltover hydrogen atom and various sites on the doped carbon. The theoretical calculations can explain the experimental results well, which also shed light on the most favorable and possible sites with which the spiltover hydrogen atoms bind. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Assignment of the Raman-active modes of the antitumor agent azathioprine by normal-mode calculationsJOURNAL OF RAMAN SPECTROSCOPY, Issue 10 2001Alberto Vivoni Azathioprine is a slow-release prodrug of 6-mercaptopurine and an established clinical agent for the treatment of human leukemias and other immunologically mediated diseases. The Raman spectra (1600,600 cm,1) of solid and solution azathiopurine were recorded and are presented along with results from normal-mode calculations. The band assignments were derived from semi-empirical and ab initio molecular orbital calculations. The ab initio calculations were performed with the restricted Hartree,Fock method and the semi-empirical methods utilized the AM1, PM3 and MNDO-d methods. Copyright © 2001 John Wiley & Sons, Ltd. [source] Is the Addition-Fragmentation Step of the RAFT Polymerisation Process Chain Length Dependent?,MACROMOLECULAR THEORY AND SIMULATIONS, Issue 5 2006Ekaterina I. Izgorodina Abstract Summary: The chain length dependence of the addition-fragmentation equilibrium constant (K) for cumyl dithiobenzoate (CDB) mediated polymerisation of styrene has been studied via high level ab initio molecular orbital calculations. The results indicate that chain length and penultimate unit effects are extremely important during the early stages of the polymerisation process. In the case of the attacking radical (i.e., R, in: R,,+,SC(Z)SR,,,,RSC,(Z)SR,), the equilibrium constant varies by over three orders of magnitude on extending R, from the styryl unimer to the trimer species and actually increases with chain length, further confirming that K is high in this system. When the reactions of the cumyl leaving group and cyanoisopropyl initiating species, which are also present in CDB-mediated polymerisation of styrene in the presence of the initiator 2,2,-azoisobutyronitrile, are also included, the variation in K extends over five orders of magnitude. Although less significant, the influence of the R, group should also be taken into account in a complete kinetic model of the RAFT process. However, for most practical purposes, its chain length effects beyond the unimer stage may be ignored. These results indicate that current simplified models of the RAFT process, which typically ignore all chain length effects in the R and R, positions, and all substituent effects in the R, position, may be inadequate, particularly in modelling the initial stages of the process. [source] Chemopreventive Action of Xanthone Derivatives on Photosensitized DNA Damage,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2005Kazutaka Hirakawa ABSTRACT Photosensitized DNA damage participates in solar-UV carcinogenesis, photogenotoxicity and phototoxicity. A chemoprevention of photosensitized DNA damage is one of the most important methods for the above phototoxic effects. In this study, the chemopreventive action of xanthone (XAN) derivatives (bellidifolin [BEL], gentiacaulein [GEN], norswertianin [NOR] and swerchirin [SWE]) on DNA damage photosensitized by riboflavin was demonstrated using [32P]-5,-end-labeled DNA fragments obtained from genes relevant to human cancer. GEN and NOR effectively inhibited the formation of piperidine-labile products at consecutive G residues by photoexcited riboflavin, whereas BEL and SWE did not show significant inhibition of DNA damage. The four XAN derivatives decrease the formation of 8-oxo-7,8-dihydro-2,-deoxyguanosine (8-oxodGuo), an oxidative product of G, by photoexcited riboflavin. The preventive action for the 8-oxodGuo formation of these XAN derivatives increased in the following order: GEN > NOR , BEL > SWE. A fluorescence spectroscopic study and ab initio molecular orbital calculations suggested that the prevention of DNA photodamage is because of the quenching of the triplet excited state of riboflavin by XAN derivatives through electron transfer. This chemoprevention is based on neither antioxidation nor a physical sunscreen effect; rather, it is based on the quenching of a photosensitizer. In conclusion, XAN derivatives, especially GEN, may act as novel chemopreventive agents by the quenching mechanism of an excited photosensitizer. [source] Amino and cyano N atoms in competitive situations: which is the best hydrogen-bond acceptor?ACTA CRYSTALLOGRAPHICA SECTION B, Issue 6 2001A crystallographic database investigation The relative hydrogen-bond acceptor abilities of amino and cyano N atoms have been investigated using data retrieved from the Cambridge Structural Database and via ab initio molecular orbital calculations. Surveys of the CSD for hydrogen bonds between HX (X = N, O) donors, N,T,C,N (push,pull nitriles) and N,(Csp3)n,C,N molecular fragments show that the hydrogen bonds are more abundant on the nitrile than on the amino nitrogen. In the push,pull family, in which T is a transmitter of resonance effects, the hydrogen-bonding ability of the cyano nitrogen is increased by conjugative interactions between the lone pair of the amino substituent and the C,N group: a clear example of resonance-assisted hydrogen bonding. The strength of the hydrogen-bonds on the cyano nitrogen in this family follows the experimental order of hydrogen-bond basicity, as observed in solution through the pKHB scale. The number of hydrogen bonds established on the amino nitrogen is greater for aliphatic aminonitriles N,(Csp3)n,C,N, but remains low. This behaviour reflects the greater sensitivity of the amino nitrogen to steric hindrance and the electron-withdrawing inductive effect compared with the cyano nitrogen. Ab initio molecular orbital calculations (B3LYP/6-31+G** level) of electrostatic potentials on the molecular surface around each nitrogen confirm the experimental observations. [source] 2-(3-Pyridyl)-1,3,8-triazanaphthalene, a product of the catalytic transformation of 3-cyanopyridineACTA CRYSTALLOGRAPHICA SECTION C, Issue 9 2003Jan Janczak The title compound, C12H8N4, was obtained by thermal treatment of 3-cyanopyridine in the presence of magnesium phthalocyanine as catalyst. The X-ray structure analysis, in direct contrast to molecular orbital calculations corresponding to the gas phase, shows the molecule to be non-planar in the solid state, with an interplanar angle between the pyridine and 1,3,8-triazanaphthalene rings of 13.33,(9)°. Molecules related to one another by cell translation, and positioned at intervals consistent with ,,, intermolecular interactions, form stacks in the b direction. [source] Molecular Structure and QSAR Study on Antispasmodic Activity of some Xanthoxyline DerivativesARCHIV DER PHARMAZIE, Issue 5 2006Rodrigo dos Santos Abstract Semi-empirical molecular orbital calculations at AM1 level were done with the aim to investigate the structure-activity relationships of antispasmodic activities of ten 2-(X-benzyloxy)-4,6-dimethoxyacetophenones with X = H, 4,-F, 4,-NO2, 4,-CH3, 4,-Cl, 3,,4,-(CH3)2, 4,-OCH3, 4,-Br, 4,-OCH2C6H5, and 4,-C(CH3)3, against acetylcholine-induced contraction of the guinea pig ileum. The most significant quantum chemical descriptors for this series of compounds were the net atomic charges, nucleophilic and electrophilic frontier electron density, HOMO and LUMO orbitals, and reactivity indices. While no significant correlations were found employing molecular parameters such as heat of formation, dipole moment, molecular polarizability, and so on, good correlations were obtained using the reactivity indices of HOMO and LUMO orbitals at specific atoms of the molecules. These results indicate that the spatial distribution of HOMO and LUMO orbitals over these specific atoms play an important role for an increase of biological activity. [source] Photofading of azo dyes: a theoretical studyCOLORATION TECHNOLOGY, Issue 3 2008Sandeep Tripathi The light fastness of a number of azo dyes has been investigated using all-valence molecular orbital methods, AM1 and PM3. The results of molecular orbital calculations are used to obtain both highest occupied molecular orbital and lowest unoccupied molecular orbital frontier electron density, which, respectively, can account for the propensity of the electrophilic and nucleophilic attack at a particular atom in a molecule. The highest occupied molecular orbital and lowest unoccupied molecular orbital superdelocalisability have also been obtained to explain the order of light fastness values in different dyes of a particular series. In addition, attempts have been made to correlate the light fastness values with the difference in energy of the highest occupied molecular orbital of the dye and the lowest unoccupied molecular orbital of the singlet oxygen. [source] | ||||||||||||||||