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Natural Bond Orbital (natural + bond_orbital)
Terms modified by Natural Bond Orbital Selected AbstractsSynthesis and vibrational analysis of N-(2,-Furyl)-ImidazoleJOURNAL OF RAMAN SPECTROSCOPY, Issue 8 2009A. E. Ledesma Abstract The N-(2,-furyl)-imidazole (1) has been prepared and characterized using infrared, Raman and multidimensional nuclear magnetic resonance spectroscopies. Theoretical calculations have been carried out by employing the Density Functional Theory (DFT) method, in order to optimize the geometry of their two conformers in the gas phase and to support the assignments of the vibrational bands of 1 to their normal modes. For a complete assignment of the compound, DFT calculations were combined with Scaled Quamtum Mecanic Force Field (SQMFF) methodology in order to fit the theoretical wavenumber values to the experimental one. Furthermore, Natural Bond Orbital (NBO) and topological properties by Atoms In Molecules (AIM) calculations were performed to analyze the nature and magnitude of the intramolecular interactions. The result reveals that two conformers are expected in liquid phase. Copyright © 2009 John Wiley & Sons, Ltd. [source] Hierarchical Structures in Tin(II) OxalatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2008Padmini Ramaswamy Abstract Six new SnII oxalates exhibiting a hierarchy of structures have been prepared employing hydrothermal methods. The compounds I [C10N2H10][Sn(C2O4)2], II [C10N2H10][Sn2(C2O4)3], and III [C8N4H26][Sn(C2O4)2]2·2H2O possess zero-dimensional molecular structures; IV [C10N2H8]2[Sn(C2O4)]2 and V [C12N2H8][SnC2O4] have one-dimensional chain structures; and compound VI [C5N2H14]2[Sn4(C2O4)6]·7H2O has a two-dimensional layer structure. The SnII ions have 4- and 6-coordination with square-pyramidal or pentagonal-bipyramidal geometry, in which the lone pair of electrons also occupies one of the vertices. Weak intermolecular forces such as hydrogen-bond interactions, ,···, interactions, and lone-pair,, interactions have been observed and appear to lendstructural stability. Theoretical studies indicate that the ,···, interaction energy between the bound 1,10-phenanthroline molecules is of the order of 5,6 kcal,mol,1 in V. Natural bond orbital (NBO) analysis on two model compounds, II and IV, indicates reasonable lone-pair,, interactions. The close structural relationship between all the compounds indicates that a building-up process from the zero-dimensional monomer can be considered. The present structures provide opportunities for evaluating the structure-directing role of the lone pair of electrons of SnII.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Natural bond orbital-based energy density analysis for correlated methods: Second-order Møller,Plesset perturbation and coupled-cluster singles and doublesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2008Yutaka Imamura Abstract Natural bond orbital-based energy density analysis (NBO-EDA), which split energies into atomic and bonding contributions, is proposed for correlated methods such as coupled-cluster singles and doubles (CCSD) and second-order Møller,Plesset (MP2) perturbation. Applying NBO-EDA for CCSD and MP2 to ethylene and the Diels,Alder reaction, we are successful in obtaining useful knowledge regarding electron correlation of ,- and ,-type orbitals, and clarifying the difference of the reaction barriers and heat of reaction calculated by CCSD and MP2. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Hydrogen bonding characterization of XH2NH2···HNO(X = B, Al, Ga) complexes: A theoretical investigationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2008Ying Liu Abstract The complexes of XH2NH2···HNO(X = B, Al, Ga) are characterized as head to tail with hydrogen bonding interactions. The structural characteristics can be confirmed by atoms in molecules (AIM) analysis, which also provide comparisons of hydrogen bonds strengths. The calculated interaction energies at G2MP2 level show that stability of complexes decrease as BH2NH2···HNO > AlH2NH2···HNO > GaH2NH2···HNO. On the basis of the vibrational frequencies calculations, there are red-shifts for ,(X1H) and blue-shifts for ,(NH) in the complexes on dihydrogen bonding formations (X1H···HN). On hydrogen bonding formations (NH···O), there are red-shifts for ,(NH) compared to the monomers. Natural bond orbital (NBO) analysis is used to discuss the reasons for the ,(X1H) and ,(NH) stretching vibrational shifts by hyperconjugation, electron density redistribution, and rehybridization. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Theoretical and vibrational spectral investigation of sodium salt of acenocoumarolJOURNAL OF RAMAN SPECTROSCOPY, Issue 8 2009I. Hubert Joe Abstract The FT-IR and FT-Raman spectra of sodium salt of 4-hydroxy-3[1-(4-nitrophenyl)-3-oxobutyl]-2H -1-benzopyran-2-one (acenocoumarol sodium salt) in solid phase have been recorded and analyzed. The optimization geometry, intramolecular hydrogen bonding, and harmonic vibrational wavenumbers of acenocoumarol sodium salt have been investigated with the help of B3LYP density functional theory (DFT) methods. The infrared and Raman spectra were predicted theoretically from the calculated intensities. Natural bond orbital (NBO) analysis indicates the presence of CH···O hydrogen bonding in the molecule. The first static hyperpolarizability of the molecule has been computed. Copyright © 2009 John Wiley & Sons, Ltd. [source] Coadsorption of trimethyl phosphine and thiocyanate on colloidal silver: a SERS study combined with theoretical calculationsJOURNAL OF RAMAN SPECTROSCOPY, Issue 4 2009Gengshen Hu Abstract The adsorption of trimethyl phosphine (TMP) on colloidal silver has been investigated by means of surface-enhanced Raman scattering spectroscopy (SERS). On the basis of surface selection rules, it is deduced from the SERS results that TMP adsorbs on silver surface via its P atom. The electron donor effect of TMP can be sensitively probed by the coadsorbed SCN,. The Raman wavenumber of ,CN of the adsorbed SCN, shifts to lower wavenumbers when TMP is coadsorbed with SCN, and the red shift of C,N stretching wavenumber is found to increase with increasing surface coverage of TMP. This could be explained in terms of the electron donor effect of TMP. Density functional theory (DFT) calculations further confirm the experimental results that the charge transfer is from TMP to silver surface rather than reversely. Natural bond orbital (NBO) analysis indicates that the red shift of C,N stretching mode is due the increase of electronic populations of ,* orbital of C,N bond induced by coadsorbed TMP, consequently the C,N bond is weakened, and the ,CN shifts to lower wavenumbers. An NBO analysis also indicates that the conjugated effect between S atom and C,N bond could easily make the charge transfer from silver surface to C,N bond. Copyright © 2008 John Wiley & Sons, Ltd. [source] Theoretical reassessment of Whelk-O1 as an enantioselective receptor for 1-(4-halogeno-phenyl)-1-ethylamine derivativesCHIRALITY, Issue S1 2004Alberto Del Rio Abstract A combination of molecular mechanics and first principles calculations was used to explore the enantioselectivity of receptors, taking into account experimental data from the CHIRBASE database. Interactions between the Whelk-O1 HPLC chiral stationary phase with the complete series of 1-(4-halogeno-phenyl)-1-ethylamine derivative racemates were studied. The objective was to extract information from the interactions between the chiral Whelk-O1 stationary phase and the enantiomers, hence probing the origin of the enantioselective behavior. Calculations correctly reproduce the elution orders and reasonably describe the experimental enantioselectivities and retention factors. Different binding modes were observed for the first eluted enantiomer complexes, whereas the second eluted show only one prevalent diastereomeric binding fashion. Natural bond orbital (NBO) analysis was used on the global minima bound-complexes to quantify donor-acceptor interactions among chiral stationary phase and ligand moieties. Intermolecular hydrogen bonding was found to be the essential energetic interaction for all systems studied. CH-,, aromatic stacking and various charge transfer interactions were found to be smaller in magnitude but still important for the global enantioselective behavior. The three-point interaction model is discussed, pointing out the difficulty of its application for the qualitative prediction of elution orders (absolute configurations). Chirality 16:S1,S11, 2004. © 2004 Wiley-Liss, Inc. [source] Valence and extra-valence orbitals in main group and transition metal bondingJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 1 2007C. R. Landis Abstract We address the issue first raised by Maseras and Morokuma with regard to the questionable treatment of empty p-orbitals in the algorithm for natural atomic/bond orbitals (NAOs, NBOs) and associated natural population analysis. We quantify this issue in terms of the numerical error (root-mean-square density deviation) resulting from the two alternative treatments of empty p-sets, leading to distinct NAOs, atomic charges, and idealized Lewis structural representations. Computational application of this criterion to a broad spectrum of main group and transition group species (employing both single- and multi-structure resonance models) reveals the interesting general pattern of (i) relatively insignificant differences for normal-valent species, where a single resonance structure is usually adequate, but (ii) clear superiority of the standard NAO algorithm for hypervalent species, where multi-resonance character is pronounced. These comparisons show how the divisive issue of "valence shell expansion" in transition metal bonding is deeply linked to competing conceptual models of hypervalency (viz., "p-orbital participation" in skeletal hybridization vs. 3c/4e resonance character). The results provide a quantitative measure of superiority both for the standard NAO evaluation of atomic charges as well as the general 3c/4e (A: B-C , A-B :C resonance) picture of main- and transition-group hypervalency. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2007 [source] Intramolecular hydrogen bond in 3-imino-propenylamine isomers: AIM and NBO studiesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2010H. Raissi Abstract The molecular structure and intramolecular hydrogen bond energy of 18 conformers of 3-imino-propenyl-amine were investigated at MP2 and B3LYP levels of theory using the standard 6-311++G** basis set. The atom in molecules or AIM theory of Bader, which is based on the topological properties of the electron density (,), was used additionally and the natural bond orbital (NBO) analysis was also carried out. Furthermore calculations for all possible conformations of 3-imino-propenyl-amin in water solution were also carried out at B3LYP/6-311++G** and MP2/6-311++G** levels of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the imine,amine conformers of this compound are more stable than the other conformers. B3LYP method predicts the IMA-1 as global minimum. This stability is mainly due to the formation of a strong NH···N intramolecular hydrogen bond, which is assisted by ,-electrons resonance, and this ,-electrons are established by NH2 functional group. Hydrogen bond energies for all conformers of 3-imino-propenyl-amine were obtained from the related rotamers methods. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Comparative study on the nonadditivity of methyl group in lithium bonding and hydrogen bondingINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2009Qingzhong Li Abstract Quantum chemical calculations at the second-order Moeller,Plesset (MP2) level with 6-311++G(d,p) basis set have been performed on the lithium-bonded and hydrogen-bonded systems. The interaction energy, binding distance, bond length, and stretch frequency in these systems have been analyzed to study the nonadditivity of methyl group in the lithium bonding and hydrogen bonding. In the complexes involving with NH3, the introduction of one methyl group into NH3 molecule results in an increase of the strength of lithium bonding and hydrogen bonding. The insertion of two methyl groups into NH3 molecule also leads to an increase of the hydrogen bonding strength but a decrease of the lithium bonding strength relative to that of the first methyl group. The addition of three methyl groups into NH3 molecule causes the strongest hydrogen bonding and the weakest lithium bonding. Although the presence of methyl group has a different influence on the lithium bonding and hydrogen bonding, a negative nonadditivity of methyl group is found in both interactions. The effect of methyl group on the lithium bonding and hydrogen bonding has also been investigated with the natural bond orbital and atoms in molecule analyses. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Development of eclipsed and staggered forms in some hydrogen bonded complexesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2009Ali Ebrahimi Abstract Intermolecular hydrogen bonding in X3CH···NH3 (X = H, F, Cl, and Br) complexes has been studied by B3LYP, B3PW91, MP2, MP3, MP4, and CCSD methods using 6-311++G(d,p) and AUG-cc-PVTZ basis sets. These complexes could exist in both eclipsed (EC) and staggered (ST) forms. The differences between binding energies of EC and ST forms are negligible and all EC and ST shapes correspond to minimum stationary states. The order of stabilities of them is in an agreement with the results of atoms in molecules (AIM) and natural bond orbital (NBO) analyses. On the basis of low differences between binding energies, ST forms are more stable than EC forms in all complexes with the exception of Br3CH···NH3, which behaves just opposite. Although the differences between binding energies are negligible, they are consistent with the results of AIM analysis. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Quantum chemical studies on molecular structural conformations and hydrated forms of salicylamide and O-hydroxybenzoyl cyanideINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 3 2005K. Anandan Abstract Ab initio and density functional theory (DFT) methods have been employed to study the molecular structural conformations and hydrated forms of both salicylamide (SAM) and O-hydroxybenzoyl cyanide (OHBC). Molecular geometries and energetics have been obtained in the gaseous phase by employing the Møller,Plesset type 2 MP2/6-311G(2d,2p) and B3LYP/6-311G(2d,2p) levels of theory. The presence of an electron-releasing group (SAM) leads to an increase in the energy of the molecular system, while the presence of an electron-withdrawing group (OHBC) drastically decreases the energy. Chemical reactivity parameters (, and ,) have been calculated using the energy values of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) obtained at the Hartree,Fock (HF)/6-311G(2d,2p) level of theory for all the conformers and the principle of maximum hardness (MHP) has been tested. The condensed Fukui functions have been calculated using the atomic charges obtained through the natural bond orbital (NBO) analysis scheme for all the optimized structures at the B3LYP/6-311G(2d,2p) level of theory, and the most reactive sites of the molecules have been identified. Nuclear magnetic resonance (NMR) studies have been carried out at the B3LYP/6-311G(2d,2p) level of theory for all the conformers in the gaseous phase on the basis of the method of Cheeseman and coworkers. The calculated chemical shift values have been used to discuss the delocalization activity of the electron clouds. The dimeric structures of the most stable conformers of both SAM and OHBC in the gaseous phase have been optimized at the B3LYP/6-311G(2d,2p) level of theory, and the interaction energies have been calculated. The most stable conformers of both compounds bear an intramolecular hydrogen bond, which gives rise to the formation of a pseudo-aromatic ring. These conformers have been allowed to interact with the water molecule. Special emphasis has been given to analysis of the intermolecular hydrogen bonds of the hydrated conformers. Self-consistent reaction field (SCRF) theory has been employed to optimize all the conformers in the aqueous phase (, = 78.39) at the B3LYP/6-311G(2d,2p) level of theory, and the solvent effect has been studied. Vibrational frequency analysis has been performed for all the optimized structures at MP2/6-311G(2d,2p) level of theory, and the stationary points corresponding to local minima without imaginary frequencies have been obtained for all the molecular structures. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Theoretical studies on the role of ,-electron delocalization in determining the conformation of N-benzylideneaniline with three types of LMO basis setsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2006Peng Bao Abstract To understand the role of ,-electron delocalization in determining the conformation of the NBA (Ph,NCH,Ph) molecule, the following three LMO (localized molecular orbital) basis sets are constructed: a LFMO (highly localized fragment molecular orbital), an NBO (natural bond orbital), and a special NBO (NBO-II) basis sets, and their localization degrees are evaluated with our suggesting index DL. Afterward, the vertical resonance energy ,EV is obtained from the Morokuma's energy partition over each of three LMO basis sets. ,EV = ,EH (one electron energy) + ,Etwo (two electron energy), and ,Etwo = ,ECou (Coulomb) + ,Eex (exchange) + ,Eec (or ,,En) (electron correction). ,EH is always stabilizing, and ,ECou is destabilizing for all time. In the case of the LFMO basis set, ,ECou is so great that ,Etwo > |,EH|. Therefore, ,EV is always destabilizing, and is least destabilizing at about the , = 90° geometry. Of the three calculation methods such as HF, DFT, and MPn (n = 2, 3, and 4), the MPn method provides ,EV with the greatest value. In the case of the NBO basis set, on the contrary, ,EV is stabilizing due to ,ECou being less destabilizing, and it is most stabilizing at a planar geometry. The LFMO basis set has the highest localization degree, and it is most appropriate for the energy partition. In the NBA molecule, ,-electron delocalization is destabilization, and it has a tendency to distort the NBA molecular away from its planar geometry as far as possible. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 809,824, 2006 [source] Substituent effects on conformational preference in , -substituted , -fluorophenylacetic acid methyl ester model systems for chiral derivatizing agentsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 10 2009Riadh Sahnoun Abstract In connection with study of chiral derivatizing agents (CDAs) for NMR determination of absolute configuration of organic compounds, factors controlling the conformational preference between syn - and anti -forms in , -substituted , -fluorophenylacetic acid methyl ester (FC(X)(Ph)COOMe) model systems were theoretically investigated. Substituents X at the stereogenic carbon atom were X,=,H, CCH and CH3, the electronic and steric properties of which were significantly different from each other. The model system with X,=,CCH and that with X,=,CH3 were found to be possible candidates for fluorine-containing CDAs. The syn conformation is stable compared with the anti one by 0.7,kcal,mol,1 for the ester with X,=,CCH. On the other hand, the anti conformation is stable compared with the syn one by 0.5,kcal,mol,1 for the ester with X,=,CH3. Both natural bond orbital (NBO) analysis and deletion of selected orbitals based on the donor,acceptor NBO scheme were adopted for semi-quantitative estimation of factors responsible for the conformational preference as well as a qualitative inspection of occupied canonical molecular orbitals (MOs). It was shown that [,,(,*,+,,*)(CO)] and [,,,*(Ph) and ,(Ph),,*] hyperconjugations are the main factors controlling the conformational preferences between the syn and anti conformations. Other types of effects such as electrostatic effects were also investigated. The role of the fluorine atom was also clarified. Copyright © 2009 John Wiley & Sons, Ltd. [source] AIM and NBO analysisMAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2010In the series of diaminoenones, large high-frequency shifts of the 1H NMR of the NH group in the cis -position relative to the carbonyl group suggests strong NH···O intramolecular hydrogen bonding comprising a six-membered chelate ring. The NH···O hydrogen bond causes an increase of the 1J(N,H) coupling constant by 2,4 Hz and high-frequency shift of the 15N signal by 9,10 ppm despite of the lengthening of the relevant NH bond. These experimental trends are substantiated by gauge-independent atomic orbital and density functional theory calculations of the shielding and coupling constants in the 3,3-bis(isopropylamino)-1-(aryl)prop-2-en-1-one (12) for conformations with the Z - and E -orientations of the carbonyl group relative to the NH group. The effects of the NH···O hydrogen-bond on the NMR parameters are analyzed with the atoms-in-molecules (AIM) and natural bond orbital (NBO) methods. The AIM method indicates a weakening of the NH···O hydrogen bond as compared with that of 1,1-di(pyrrol-2-yl)-2-formylethene (13) where NH···O hydrogen bridge establishes a seven-membered chelate ring, and the corresponding 1J(N,H) coupling constant decreases. The NBO method reveals that the LP(O) ,,*NH hyperconjugative interaction is weakened on going from the six-membered chelate ring to the seven-membered one due to a more bent hydrogen bond in the former case. A dominating effect of the NH bond rehybridization, owing to an electrostatic term in the hydrogen bonding, seems to provide an increase of the 1J(N,H) value as a consequence of the NH···O hydrogen bonding in the studied diaminoenones. Copyright © 2010 John Wiley & Sons, Ltd. [source] The effect of carbonyl group in the asymmetry of 3, 4JCH coupling constants in norbornanonesMAGNETIC RESONANCE IN CHEMISTRY, Issue 2 2008Francisco P. dos Santos Abstract A rationalization of the known difference between the 3, 4J and 3, 4J couplings transmitted mainly through the 7-bridge in norbornanone is presented in terms of the effects of hyperconjugative interactions involving the carbonyl group. Theoretical and experimental studies of 3, 4JCH couplings were carried out in 3- endo - and 3- exo -X-2-norbornanone derivatives (X = Cl, Br) and in exo - and endo -2-noborneol compounds. Hyperconjugative interactions were studied with the natural bond orbital (NBO) method. Hyperconjugative interactions involving the carbonyl ,* and ,* antibonding orbitals produce a decrease of three-bond contribution to both 3, 4J and 3, 4J couplings. However, the latter antibonding orbital also undergoes a strong , , ,* interaction, which defines an additional coupling pathway for 3, 4J but not for 3, 4J. This pathway is similar to that known for homoallylic couplings, the only difference being the nature of the intermediate antibonding orbital; i.e. for 3, 4J it is of ,*-type, while in homoallylic couplings it is of ,*-type. Copyright © 2007 John Wiley & Sons, Ltd. [source] Computation and analysis of 19F substituent chemical shifts of some bridgehead-substituted polycyclic alkyl fluoridesMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2003William Adcock Abstract The 19F NMR shieldings for several remotely substituted rigid polycyclic alkyl fluorides with common sets of substituents covering a wide range of electronic effects were calculated using the DFT-GIAO theoretical model. The level of theory, B3LYP/6,311+G(2d,p), was chosen based on trial calculations which gave good agreement with experimental values where known. The optimized geometries were used to obtain various molecular parameters (fluorine natural charges, electron occupancies on fluorine of lone pairs and of the CF bond, and hybridization states) by means of natural bond orbital (NBO) analysis which could help in understanding electronic transmission mechanisms underlying 19F substituent chemical shifts (SCS) in these systems. Linear regression analysis was employed to explore the relationship between the calculated 19F SCS and polar substituent constants and also the NBO derived molecular parameters. The 19F SCS are best described by an electronegativity parameter. The most pertinent molecular parameters appear to be the occupation number of the NBO p-type fluorine lone pair and the occupation number of the CF antibonding orbital. This trend suggests that in these types of rigid saturated systems hyperconjugative interactions play a key role in determining the 19F SCS. Electrostatic field effects appear to be relatively unimportant. Copyright © 2003 John Wiley & Sons, Ltd. [source] (E)-Methyl 2-[(2-fluorophenyl)aminomethylene]-3-oxobutanoate: X-ray and density functional theory (DFT) studyACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2009Vratislav Langer The title compound, C12H12FNO3, a potential precursor for fluoroquinoline synthesis, is essentially planar, with the most outlying atoms displaced from the best-plane fit through all non-H atoms by 0.163,(2) and 0.118,(2),Å. Molecules are arranged in layers oriented parallel to the (011) plane. The arrangement of the molecules in the structure is controlled mainly by electrostatic interactions, as the dipole moment of the molecule is 5.2,D. In addition, the molecules are linked by a weak C,H...O hydrogen bond which gives rise to chains with the base vector [1,1,1]. Electron transfer within the molecule is analysed using natural bond orbital (NBO) analysis. Deviations from the ideal molecular geometry are explained by the concept of non-equivalent hybrid orbitals. [source] Coherent superposition of resonance wave function in terms of weighted orthogonalized natural localized configurationsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2008A. H. Pakiari Abstract In this research, the projection technique has been applied in order to decompose the electronic wave function into its weighted orthogonalized resonance components. These components have been constructed by determinants whose orbitals are selected among natural bond orbitals. However, the procedure is general and any other localized orbitals can be used as well. Both , and , delocalize systems have been considered in order to check the reliability of the calculated resonance weights. For ,-systems, the presented procedure could predict significant decrease of weight of certain resonance structures when the molecular planarity was destroyed. Water cyclic clusters were also tested and the results confirmed the existence of strong ,-delocalization in the clusters. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] The behavior of transition metal nitrido bonds towards protonation rationalized by means of localized bonding schemes and their weightsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2005Vinzenz Bachler Abstract A new computational scheme is applied to rationalize the different protonation behaviors of the nitrido complexes [L,MnV(N)(acac)]+, [LCrV(N)(acac)]+, and [LVV(N)(acac)]+. L and L, represent the macrocycles 1,4,7-triazacyclononane and its N-methylated derivative, respectively, and acac is the bidentate monoanion pentane-2,4-dionate. The bonds of the complexes are partitioned into bonds to be investigated and bonds of lesser interest. The investigated bonds are the transition metal nitrido bonds MVN| (M = Mn, Cr, and V) and the bonds of lesser interest are located in the ligands. The ligand bonds are described by means of the strongly occupied natural bond orbitals. The electrons in the MVN| nitrido bonds, however, are treated more accurately. A full configuration interaction procedure is applied in the space spanned by the strongly occupied natural bond orbitals and their corresponding antibonding orbitals. Localized bonding schemes and their weights are obtained for the d, -p, bonds of interest. This is achieved by representing the two-center natural bond orbitals for a d, -p, bond by the one-center natural hybrid orbitals localized at the bond atoms. The obtained bonding schemes are close to orthogonal valence bond structures. Their weights indicate that the nitrido nitrogen in [LVV(N)(acac)]+ is more easily protonated than the nitrido nitrogens in [L,MnV(N)(acac)]+ and [LCrV(N)(acac)]+. This result is in good accord with experiment. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 532,551, 2005 [source] 2-{[(3-Fluorophenyl)amino]methylidene}-3-oxobutanenitrile and 5-{[(3-fluorophenyl)amino]methylidene}-2,2-dimethyl-1,3-dioxane-4,6-dione: X-ray and DFT studiesACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2010Vratislav Langer In the crystal structures of the title compounds, C11H9FN2O, (I), and C13H12FNO4, (II), the molecules are joined pairwise via different hydrogen bonds and the constituent pairs are crosslinked by weak C,H...O hydrogen bonds. The basic structural motif in (I), which is partially disordered, comprises pairs of molecules arranged in an antiparallel fashion which enables C,H...N[triple-bond]C interactions. The pairs of molecules are crosslinked by two weak C,H...O hydrogen bonds. The constituent pair in (II) is formed by intramolecular bifurcated C,H...O/O, and combined inter- and intramolecular N,H...O hydrogen bonds. In both structures, F atoms form weak C,F...H,C interactions with the H atoms of the two neighbouring methyl groups, the H...F separations being 2.59/2.80 and 2.63/2.71,Å in (I) and (II), respectively. The bond orders in the molecules, estimated using the natural bond orbitals (NBO) formalism, correlate with the changes in bond lengths. Deviations from the ideal molecular geometry are explained by the concept of non-equivalent hybrid orbitals. The existence of possible conformers of (I) and (II) is analysed by molecular calculations at the B3LYP/6,31+G** level of theory. [source] Hydrogen bonds assisted by ,-electron delocalization , the influence of external intermolecular interactions on dimer of formic acidJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 7-8 2008awomir J. Grabowski Abstract MP2 and DFT calculations with the use of 6-311++G(d,p) basis set were carried out to study formic acid dimer as well as this species interacting with additional Lewis acids such as HF, Li+ and Na+. These Lewis acids were positioned near carbonyl or hydroxyl oxygen atoms and their influence on geometrical and other parameters of formic acid dimer was analysed. Additionally the ,quantum theory of atoms in molecules' (QTAIM) was applied as well as the ,natural bond orbitals' (NBO) method. Numerous correlations between geometrical, QTAIM and energetic parameters were found. It was found that ,-electron delocalization is not always connected with the enhancement of H-bond strength. Copyright © 2008 John Wiley & Sons, Ltd. [source] | ||||||||||