Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.

Mass spectrometry study combined with theoretical calculation on the unimolecular fragmentation of tetrahydroimidazole-substituted methylene beta-diketones

Studies of low-energy collision-induced dissociation and isotopic labeling on ionized tetrahydroimidazole-substituted methylene P-diketones by tandem mass spectrometry showed that their unimolecular fragmentations may involve the reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms were proved by semiemipirical calculations of PM3 and AM1 methods.

Theoretical investigation of LaC3n+ (n = 0, 1, 2) clusters by density functional theory

LaC3n+ (n = 0, 1, 2) clusters have been studied using B3LYP (Becke 3-parameter-Lee-Yang-Parr) density functional method. The basis set is Dunning/ Huzinaga valence double zeta for carbon and [2s2p2d] for lanthanum, denoted LANL1DZ. Four isomers are presented for each cluster; two of them are edge binding isomers with C-2 upsilon symmetry, the other two are Linear chains with C-infinity upsilon symmetry. Meanwhile, two spin states for each isomer, that is, singlet and triplet for LaC3+, doublet and quartet for LaC3 and LaC32+, respectively, are also considered. Geometries, vibrational frequencies, infrared intensities, and other quantities are reported and discussed. The results indicate that at some spin states; the C-2 upsilon symmetry isomers are the dominant structures, while for the other spin states, linear isomers are energetically favored. (C) 1998 John Wiley & Sons, Inc.

Theoretical study on the unimolecular fragmentation of ionized tetrahydroimidazole-substituted methylene beta-diketones

Semiempirical molecular orbital calculations on the unimolecular mass spectrometric fragmentation of tetrahydroimidazole-substituted methylene beta-diketones are carried out by Austin Model 1 method, and the calculated results give a strong support to our experimental results reported previously. The optimum of the investigated molecular configuration indicates that the two hydrogen atoms attached to nitrogen atom have different activities due to their chemical environment; the relative energies of the ions in fragmentation pathway of ionized tetrahydroimidazole-substituted methylene beta-diketones provide indirectly an evidence for both the existence of ion/neutral complex and the stabilities of these ions.

THEORETICAL-ANALYSIS OF NERNSTIAN PLOTS IN THE THIN-LAYER SPECTROPOTENTIOSTATIC TECHNIQUE

The Nernstian plots in a spectropotentiostatic experiment for complex electrode processes were studied theoretically. The plots are linear for an electron transfer process coupled with a preceding or succeeding chemical reaction, and the electron stoichio

A STUDY ON CH5O+ IONS IN GAS PHASE CID EYPERIMENT AND QUANTUM CHEMISTRY CALCULATION

The structures of CH5O+ from two different reactions which are protonation of CH3OH from the above two pathways possess the same structures, CH3OH2+. The value of kinetic energy release for the metastable decomposition CH2OH3+-> CH2OH+ + H-2 determined from the experiment is in good agreement with that from theoretical calculations. The transition state of above reaction were disscussed.

Theoretical investigation on the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111) surface

In this paper, the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111) surface were investigated by using cluster (Gaussian 03) and periodic (DMol(3)) ab initio calculations. Si(111) surface was described with cluster models (Si14H17 and Si22H21) and a four-silicon layer slab with periodic boundary conditions. The effect of basis set superposition error (BSSE) was taken into account by applying the counterpoise correction. The calculated results indicated that the binding energies between hydrated Ag+ cations and clean Si(111) surface are large, suggesting a strong interaction between hydrated Ag+ cations and the semiconductor surface. With the increase of number, water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Ag+ cation. The Ag+ cation in aqueous solution will safely attach to the clean Si(111) surface.

Theoretical study on adsorption of Na+ and Na+(H2O)(n) (n=1-6) on a clean Si(111) surface

To model the adsorption of Na+ in aqueous solution on the semiconductor surface, the interactions of Na+ and Na+(H2O)(n) (n = 1-6) with a clean Si(111) surface were investigated by using hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The Si(111) surface was described with Si8H12, Si16H20, and Si22H21 Cluster models. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise (CP) correction. The calculated results indicated that the interactions between the Na+ cation and the dangling bonds of the Si(111) surface are primarily electrostatic with partial orbital interactions. The magnitude of the binding energies depends weakly on the adsorption sites and the size of the clusters. When water molecules are present, the interaction between the Nal and Si(I 11) surfaces weakens and the binding energy has the tendency to saturate. On a Si22H21 cluster described surface, the optimized Na+-surface distance for Na+(H2O)(5) adsorbed at on-top site is 4.16 angstrom and the CP-corrected binding energy (MP2) is -35.4 kJ/mol, implying a weakly adsorption of hydrated Na+ cation on clean Si(111) surface.

Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

Theoretical study of determining orientation and alignment of symmetric top molecule using laser-induced fluorescence

General expressions used for extracting the orientation and alignment parameters of a symmetric top molecule from laser-induced fluorescence (LIF) intensity are derived by employing the density matrix approach. The molecular orientation and alignment are described by molecular state multipoles. Excitation and detection are circularly and linearly polarized lights, respectively. In general cases, the LIF intensity is a complex function of the initial molecular state multipoles, the dynamic factors and the excitation-detection geometrical factors. It contains a population, ten orientation and fourteen alignment multipoles. The problem of how to extract the initial molecular state multipoles from the resolved LIF intensity is discussed.