Search results for "Ab initio"
showing 10 items of 990 documents
Scope and Limitations of Baird's Theory on Triplet State Aromaticity: Application to the Tuning of Singlet–Triplet Energy Gaps in Fulvenes
2007
Utilizing Baird's theory on triplet state aromaticity, we show that the singlet-triplet energy gaps (DeltaE(ST)) of pentafulvenes are easily varied through substitution by as much as 36 kcal mol(-1). This exploits the fact that fulvenes act as aromatic chameleons in which the dipoles reverse on going from the singlet ground state (S(0)) to the lowest pipi* triplet state (T1); thus, their electron distributions are adapted so as to achieve some aromaticity in both states. The results are based on quantum chemical calculations with the OLYP density functional theory method and the CASPT2 ab initio method, as well as spectroscopic determination of DeltaE(ST) by triplet sensitization. The findi…
"Identification of mixed bromidochloridotellurate anions in disordered crystal structures of (bdmim)2[TeX2Y4] (X, Y = Br, Cl; bdmim = 1-butyl-2,3-dim…
2013
Abstract The discrete mixed [TeBrxCl6−x]2− anions in their disordered crystal structures have been identified by using the phases prepared by the reaction of 1-butyl-2,3-dimethylimidazolium halogenides (bdmim)X with tellurium tetrahalogenides TeX4 (X = Cl, Br) as examples. Homoleptic (bdmim)2[TeX6] [X = Cl (1), Br (2)] and mixed (bdmim)2[TeBr2Cl4] (3), and (bdmim)2[TeBr4Cl2] (4) are formed depending on the choice of the reagents, and their crystal structures have been determined by single-crystal X-ray diffraction. The coordination environments of tellurium in all hexahalogenidotellurates are almost octahedral. Because of the crystallographic disorder, the mixed [TeBr2Cl4]2− and [TeBr4Cl2]2…
Island Homoaromaticity in the W-Shaped 2,4-Diphospha-3-arsapentadienide Anion and Related Compounds - Theoretical and Experimental Investigations
2012
A series of anions with general formula (R2C=P)2Pn– (Pn = N, P, As, Sb; R = H, Me, CF3, SiH3, SiMe3, SiF3) was investigated theoretically at the DFT (RI-BP86/TZVP) and RI-MP2/TZVP levels of approximation. Significantly sharpened central PPnP bond angles were predicted for the species with π-acceptor R substituents. The corresponding bond angle values decrease in the order Pn = N >> P > As > Sb. This finding is in agreement with the previously published structural data for [(Me3Si)2C=P]2P–. An island homoaromaticity was proposed as a suitable explanation for the observed effect. In more detail, it consists of shifting negative charge to the electron-withdrawing terminal groups with formation…
Dynamic magnetic materials based on the cationic coordination polymer [Cu(btix)2]n(2n+) [btix = 1,4-bis(triazol-1-ylmethyl)benzene]: tuning the struc…
2012
A three-dimensional coordination polymer, [Cu(btix)(2)(BF(4))(2)](n) [btix = 1,4-bis(triazol-1-ylmethyl)benzene], with antiferromagnetic interactions occurring via the organic ligand, has been prepared and characterized. It has been shown to permit the exchange of anionic species in the crystalline network with modification of the magnetic properties. Coordinated BF(4)(-) can be reversibly exchanged by different anions with (NO(3)(-) and Cl(-)) or without (PF(6)(-) and ClO(4)(-)) dynamic response of the organic ligand, which acts as the only linker between the metal centers. Interestingly, an irreversible exchange occurs with N(3)(-) anions to generate a new coordination polymer, [Cu(btix)(…
A new force field including charge directionality for TMAO in aqueous solution
2016
We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (OTMAO) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around OTMAO to mimic the OTMAO lone pairs and we migrate the negative charge on the OTMAO to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasing TMAO concentration quantitatively. The simple procedure of the…
Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution
2015
Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientatio…
Calculation of the relative basicities of methylamines in solution
1990
Abstract The relative basicities in solution of the methylamines have been calculated using the model of Miertus, Scrocco and Tomasi to describe the solvent effect. The surface of the cavity is defined with the GEPOL method. The ab initio calculations have been performed using a 4-31G basis set. The relative order is reproduced using a combination of the gas-phase proton affinities obtained with quantum-mechanical methods by Eades, Weil, Dixon and Douglass and the solvation values obtained by us. The results seem to point out that the irregular order is not due to solvent but to basis-set effects.
Matrix-isolation and ab initio study of the complex between formic acid and xenon
2012
Abstract We report on the identification of the complexes of formic acid (FA) and Xe in an argon matrix. The geometries, interaction energies, reaction barriers, and vibrational spectra of the FA⋯Xe complexes are calculated at the MP2 level of theory. The calculations reveal four structures for the trans-FA⋯Xe complex and four structures for the cis-FA⋯Xe complex. In the experiments, two structures of the trans-FA⋯Xe complex are observed after deposition of FA/Xe/Ar matrices, with and without OH⋯Xe interaction (H-bonded and non-H-bonded structures). The cis-FA⋯Xe complex was synthesized by vibrational excitation of the non-H-bonded trans-FA⋯Xe complex. The non-H-bonded and H-bonded structur…
Application of SQMFF Vibrational Calculations to Transition States: DFT and ab Initio Study of the Kinetics of Methyl Azide and Ethyl Azide Thermoly…
1998
DFT including nonlocal corrections and ab initio calculations at MP2 and MP4 levels of theory have been performed in order to provide information concerning the mechanism of the rate limiting step of the thermal decomposition of methyl azide and ethyl azide. The chemically interesting points of the ground-state potential energy surface have been fully optimized, and a detailed normal-mode analysis for the reagents and the transition states is presented. The well-established scaled quantum mechanical force field method has been used to obtain reliable vibrational frequencies for these molecular structures. The force fields of transition states have been modified by using the scale factors co…
Modeling of Point Defects in Corundum Crystals
1994
Several different approaches including Hartree-Fock ab initio cluster calculations, semiempirical INDO calculations, and atom-atom potentials were used for modeling of the spatial and electronic structure as well as migration mechanisms of both intrinsic defects (self-trapped and defect-trapped holes, O and Al vacancies) and impurities (transition-metal ions like Co, Fe, Mg, Mn, Ti). The atomic structure of all hole centers is found to be similar to V[sub K] centers in alkali halides (two-site model); their formation is energetically favorable. The energy required for 60[degree] hole reorientations inside the basic oxygen triangles is found to be similar to both the energy for hops between …