Electron donor-acceptor complex of ICl with diethyl ether - He I photoelectron spectroscopy and ab initio molecular orbital study

The He I photoelectron spectrum of the diethyl ether-ICl complex has been obtained. The oxygen orbitals are shifted to higher binding energies and that of ICl to lower binding energies owing to complex formation. Ab initio molecular orbital (MO) calculations of the complex molecule showed that the bonding is between the sigma-type lone pair of oxygen and the I atom and that the complex has C-2v symmetry. The binding energy of the complex is computed to be 8.06 kcal mol(-1) at the MP2/3-21G* level. The orbital energies obtained from the photoelectron spectra of the complex are compared and assigned with orbital energies obtained by MO calculations. Natural bond orbital analysis (NBO) shows that charge transfer is from the sigma-type oxygen lone pair to the iodine atom and the magnitude of charge transfer is 0.0744 e.

UVPES and ab initio molecular orbital studies on the electron donor-acceptor complexes of bromine with methylamines

The He I photoelectron spectra of bromine, methylamine, and their complex have been obtained, and the spectra show that lone-pair orbital energy of nitrogen in methylamine is stabilized by 1.8 eV and the bromine orbital energies are destabilized by about 0.5 eV due to complexation. Ab initio calculations have been performed on the charge-transfer complexes of Br-2 with ammonia and methyl-, dimethyl-, and trimethylamines at the 3-21G*, 6-311G, and 6-311G* levels and also with effective core potentials. Calculations predict donor and acceptor orbital energy shifts upon complexation, and there is a reasonable agreement between the calculated and experimental results. Complexation energies have been corrected for BSSE. Frequency analysis has confirmed that ammonia and trimethylamine form complexes with C-3v symmetry and methylamine and dimethylamine with C-s symmetry. Calculations reveal that the lone-pair orbital of nitrogen in amine and the sigma* orbital of Br-2 are involved in the charge-transfer interaction. LANL1DZ basis seems to be consistent and give a reliable estimate of the complexation energy. The computed complexation energies, orbital energy shifts, and natural bond orbital analysis show that the strength of the complex gradually increases from ammonia to trimethylamine.

Ab initio studies of solvent effect on conformational equilibria and vibrational spectra of dipropionamide

Systematic ab initio molecular orbital studies of the conformational equilibria and vibrational spectra of dipropionamide using the basis sets 6-31g(d) and 6-31++G(d,p) have been carried out. The vibrational spectra of dipropionamide have been satisfactorily interpreted taking into account the agreement between the calculated frequencies, infrared and Raman band intensities and the shifts in the spectra of deuterated molecules with those observed. The previous assignments of most of the vibrational bands are well confirmed, a few bands need reassignment, however. The solvent effects were investigated by self-consistent reaction field theory using dipole and self-consistent isodensity polarized continuum model methods. The introduction of a dielectric medium has only a marginal effect on the conformational equilibria and vibrational spectra. However, the calculated changes in geometry and vibrational spectra on going from the gas phase to the solution phase are in accord with the increasing weight of the dipolar resonance structure in polar solvents. (C) 2002 Elsevier Science B.V. All rights reserved.

An ab-initio study of the role of lone pairs in the structure and insulator-metal transition in SnO and PbO

We have performed density functional calculations on tetragonal SnO and PbO (litharge) in the space group P4/nmm with the specific intention of examining the role played by Sn 5s and Pb 6s lone pairs in stabilizing the structure, and in giving rise to semi-metallic behavior (of SnO at ambient pressure and of PbO in the gamma phase). Use of the electron localization function has permitted real-space visualization of the lone pair in these structures. We also discuss the electronic structure of the orthorhombic PbO (massicot, space group Pbma) which again has localized lone pairs, contrary to some earlier expectation. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Ab initio study of disorder effects on the electronic and magnetic structure of Sr2FeMoO6

We have investigated the electronic structure of ordered and disordered Sr2FeMoO6 using ab initio bandstructure methods. The effect of disorder was simulated within supercell calculations to realize several configurations with mis-site disorders. It is found that such disorder effects destroy the half-metallic ferromagnetic state of the ordered compound. It also leads to a substantial reduction of the magnetic moments at the Fe sites in the disordered configurations. Most interestingly, it is found for the disordered configurations that the magnetic coupling within the Fe sublattice as well as that within the Mo sublattice always remain ferromagnetic, while the two sublattices couple antiferromagnetically, in close analogy to the magnetic structure of the ordered compound, but,in contrast to recent suggestions.

Unimolecular HCl elimination from 1,2-dichloroethane: A single pulse shock tube and ab initio study

Thermal decomposition of 1,2-dichloroethane (1,2-DCE) has been studied in the temperature range of 10501175 K behind reflected shock waves in a single pulse shock tube. The unimolecular elimination of HCl is found to be the major channel through which 1,2-DCE decomposes under these conditions. The rate constant for the unimolecular elimination of HCl from 1,2-dichloroethane is found to be 10(13.98+/-0.80) exp(-57.8+/-2.0/RT) s(-1), where the activation energy is given in kcal mol(-1) and is very close to that value for CH3CH2Cl (EC). Ab initio (HF and MP2) and DFT calculations have been carried out to find the activation barrier and the structure of the transition state for this reaction channel from both EC and 1,2-DCE. The preexponential factors calculated at various levels of theory (BF/6-311++G**, MP2/6-311++G**, and B3LYP/6-311++G**) are (approximate to10(15) s(-1)) significantly larger than the experimental results. If the torsional mode in the ground state is treated as free internal rotation the preexponential factors reduce significantly, giving excellent agreement with experimental values. The DFT results are in excellent (fortuitous?) agreement with the experimental value for activation energy for 1,2-DCE while the MP2 and HF results seem to overestimate the barrier. However, DFT results for EC is 4.5 kcal mol(-1) less than the previously reported experimental values. At all levels, theory predicts an increase in HCI elimination barrier on beta-Cl substitution on EC.

Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl

This paper reports ab intio, DFT and transition state theory (TST) calculations on HF, HCI and CIF elimination reactions from CH2Cl-CH2F molecule. Both the ground state and the transition state for HX elimination reactions have been optimized at HF, MP2 and DFT calculations with 6-31G*, 6-31G** and 6-311++G** basis sets. In addition, CCSD(T) single point calculations were carried out with MP2/6-311++G** optimized geometry for more accurate determination of the energies of the minima and transition state, compared to the other methods employed here. Classical barriers are converted to Arrhenius activation energy by TST calculations for comparisons with experimental results. The pre-exponential factors, A, calculated at all levels of theory are significantly larger than the experimental values. For activation energy, E-a DFT gives good results for HF elimination, within 4-8 W mol(-1) from experimental values. None of the methods employed, including CCSD(T), give comparable results for HCI elimination reactions. However, rate constants calculated by CCSD(T) method are in very good agreement with experiment for HCI elimination and they are in reasonable agreement for HF elimination reactions. Due to the strong correlation between A and E., the rate constants could be fit to a lower A and E-a (as given by experimental fitting, corresponding to a tight TS) or to larger A and E-a (as given by high level ab initio calculations, corresponding to a loose TS). The barrier for CIF elimination is determined to be 607 U mol(-1) at HF level and it is unlikely to be important for CH2FCH2Cl. Results for other CH2X-CH2Y (X,Y = F/Cl) are included for comparison.

Thermal decomposition of haloethanols: single pulse shock tube and ab initio studies

This paper reports single pulse shock tube and ab initio studies on thermal decomposition of 2-fluoro and 2-chloroethanol at T=1000–1200 K. Both molecules have HX (X = F/Cl) and H2O molecular elimination channels. The CH3CHO formed by HX elimination is chemically active and undergoes secondary decomposition resulting in the formation of CH4, C2H6, and C2H4. A detailed kinetic simulation indicates that the formation of C2H4 could not be quantitatively explained as arising exclusively from secondary CH3CHO decomposition. Contributions from primary radical processes need to be considered to explain C2H4 quantitatively. Ab initio calculations on HX and H2O elimination reactions from the haloethanols at HF, MP2, and DFT levels with various basis sets up to 6/311++G**are reported. It is pointed out that due to strong correlations between A and Eα, comparison of these two parameters between experimental and theoretical results could be misleading.

Relation between the work function and Young's modulus of RhSi and estimate of Schottky-barrier height at RhSi/Si interface: An ab-initio study

Density-functional calculations are performed to explore the relationship between the work function and Young's modulus of RhSi, and to estimate the p-Schottky-barrier height (SBH) at the Si/RhSi(010) interface. It is shown that the Young's modulus and the workfunction of RhSi satisfy the generic sextic relation, proposed recently for elemental metals. The calculated p-SBH at the Si/RhSi interface is found to differ only by 0.04 eV in opposite limits, viz., no-pinning and strong pinning. We find that the p-SBH is reduced as much as by 0.28 eV due to vacancies at the interface. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4761994]

Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

Thermal decomposition of propargyl alcohol (C3H3OH), a molecule of interest in interstellar chemistry and combustion, was investigated using a single pulse shock tube in the temperature ranging from 953 to 1262 K. The products identified include acetylene, propyne, vinylacetylene, propynal, propenal, and benzene. The experimentally observed overall rate constant for thermal decomposition of propargyl alcohol was found to be k = 10((10.17 +/- 0.36)) exp(-39.70 +/- 1.83)/RT) s(-1) Ab initio theoretical calculations were carried out to understand the potential energy surfaces involved in the primary and secondary steps of propargyl alcohol thermal decomposition. Transition state theory was used to predict the rate constants, which were then used and refined in a kinetic simulation of the product profile. The first step in the decomposition is C-O bond dissociation, leading to the formation of two important radicals in combustion, OH and propargyl. This has been used to study the reverse OH propargyl radical reaction, about which there appears to be no prior work. Depending on the site of attack, this reaction leads to propargyl alcohol or propenal, one of the major products at temperatures below 1200 K. A detailed mechanism has been derived to explain all the observed products.

Dissociation Constants of Weak Acids from ab Initio Molecular Dynamics Using Metadynamics: Influence of the Inductive Effect and Hydrogen Bonding on pK(a) Values

The theoretical estimation of the dissociation constant, or pK(a), of weak acids continues to be a challenging field. Here, we show that ab initio CarParrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free-energy profile of the dissociation reaction provide reasonable estimates of the pK(a) value. Water molecules, sufficient to complete the three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid, and the difference in their values provides the estimate for pK(a). We show for a series of organic acids that CPMD simulations in conjunction with metadynamics can provide reasonable estimates of pK(a) values. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cis- and trans-butenedioic acid, and the isomers of hydroxybenzoic acid. These systems were chosen to highlight that the procedure could correctly account for the influence of the inductive effect as well as hydrogen bonding on pK(a) values of weak organic acids. In both situations, the CPMD metadynamics procedure faithfully reproduces the experimentally observed trend and the magnitudes of the pK(a) values.

Pt-Poisoning-Free Efficient CO Oxidation on Pt3Co Supported on MgO(100): An Ab Initio Study

Late-transition-metal-doped Pt clusters are prevalent in CO oxidation catalysis, as they exhibit better catalytic activity than pure Pt, while reducing the effective cost and poisoning However, completely eliminating the critical problem of Pt poisoning still poses a big challenge. Here, we report for the first time that, among the bimetallic clusters ((Pt3M where M = Co, Ni, and Cu)/MgO(100)), the CO adsorption site inverts for Pt3Co/MgO(100) from Pt to Co, due to the complete uptake of Pt d-states by lattice oxygen. While this resolves the problem of Pt poisoning, good reaction kinetics are predicted through low barriers for Langmuir-Hinshelwood and Mars van Krevelen (MvK) mechanisms of CO oxidation for Pt3Co/MgO(100) and Li-doped MgO(100), respectively. Li doping in MgO(100) compensates for the charge imbalance caused by a spontaneous oxygen vacancy formation. Pt-3 Co/Li-doped MgO(100) stands out as an exceptional CO oxidation catalyst, giving an MvK reaction barrier as low as 0.11 eV. We thereby propose a novel design strategy of d-band center inversion for CO oxidation catalysts with no Pt poisoning and excellent reaction kinetics.

Estimating successive pK(a) values of polyprotic acids from ab initio molecular dynamics using metadynamics: the dissociation of phthalic acid and its isomers

Estimation of the dissociation constant, or pK(a), of weak acids continues to be a central goal in theoretical chemistry. Here we show that ab initio Car-Parrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free energy profile of the dissociation reaction can provide reasonable estimates of the successive pK(a) values of polyprotic acids. We use the distance-dependent coordination number of the protons bound to the hydroxyl oxygen of the carboxylic group as the collective variable to explore the free energy profile of the dissociation process. Water molecules, sufficient to complete three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. Two distinct minima corresponding to the dissociated and un-dissociated states of the acid are observed and the difference in their free energy values provides the estimate for pK(a), the acid dissociation constant. We show that the method predicts the pK(a) value of benzoic acid in good agreement with experiment and then show using phthalic acid (benzene dicarboxylic acid) as a test system that both the first and second pK(a) values as well, as the subtle difference in their values for different isomers can be predicted in reasonable agreement with experimental data.

Ab Initio Molecular Dynamics Simulations of Amino Acids in Aqueous Solutions: Estimating pK(a) Values from Metadynamics Sampling

Changes in the protonation and deprotonation of amino acid residues in proteins play a key role in many biological processes and pathways. Here, we report calculations of the free-energy profile for the protonation deprotonation reaction of the 20 canonical alpha amino acids in aqueous solutions using ab initio Car-Parrinello molecular dynamics simulations coupled with metad-ynamics sampling. We show here that the calculated change in free energy of the dissociation reaction provides estimates of the multiple pK(a) values of the amino acids that are in good agreement with experiment. We use the bond-length-dependent number of the protons coordinated to the hydroxyl oxygen of the carboxylic and the amine groups as the collective variables to explore the free-energy profiles of the Bronsted acid-base chemistry of amino acids in aqueous solutions. We ensure that the amino acid undergoing dissociation is solvated by at least three hydrations shells with all water molecules included in the simulations. The method works equally well for amino acids with neutral, acidic and basic side chains and provides estimates of the multiple pK(a) values with a mean relative error, with respect to experimental results, of 0.2 pK(a) units.