Analytical Potential Energy Function for the Ground State X^{1} Sigma^+ of LaCl

The equilibrium geometry, harmonic frequency and dissociation energy of lanthanum monochloride have been calculated at B3LYP, MP2, QCISD(T) levels with energy-consistent relativistic effective core potentials. The possible electronic state and reasonable dissociation limit for the ground state are determined based on atomic and molecular reaction statics. Potential energy curve scans for the ground state X^{1} Sigma^+ have been carried out with B3LYP and QCISD(T) methods due to their better performance in bond energy calculations. We find the potential energy calculated with QCISD(T) method is about 0.5 eV larger than dissociation energy when the diatomic distance is as large as 0.8 nm. The problem that single-reference ab initio methods don't meet dissociation limit during calculations of lanthanide heavy-metal elements is analyzed. We propose the calculation scheme to derive analytical Murrell-Sorbie potential energy function and Dunham expansion at equilibrium position. Spectroscopic constants got by standard Dunham treatment are in good agreement with results of rotational analyses on spectroscopic experiments. The analytical function is of much realistic importance since it is possible to be applied to predict fine transitional structure and study reaction dynamic process.Comment: 10 pages, 1 figure, 3 table

Prediction of bond dissociation energies and transition state barriers by a modified complete basis set model chemistry

The complete basis set model chemistries CBS-4 and CBS-q were modified using density functional theory for the geometry optimization step of these methods. The accuracy of predicted bond dissociation energies and transition state barrier heights was investigated based on geometry optimizations using the B3LYP functional with basis set sizes ranging from 3-21G(d,p) to 6-311G(d,p). Transition state barrier heights can be obtained at CBS-q with B3LYP/6-31G(d,p) geometries with rms error of 1.7 kcal/mol within a test set of ten transition state species. The method should be applicable to molecules with up to eight or more heavy atoms. Use of B3LYP/6-311G(d,p) for geometry optimizations leads to further improvement of CBS-q barrier heights with a rms error of 1.4 kcal/mol. For reference, the CBS-QCI/APNO model chemistry was evaluated and is shown to provide very reliable predictions of barrier heights (rms error=1.0 kcal/mol)

On the ground electronic states of copper silicide and its ions

The low-lying electronic states of SiCu, SiCu^+, and SiCu^− have been studied using a variety of high-level ab initio techniques. As expected on the basis of simple orbital occupancy and bond forming for Si(s^2p^2)+Cu(s^1) species, ^2Π_r, ^1Σ^+, and ^3Σ^− states were found to be the ground electronic states for SiCu, SiCu^+, and SiCu^−, respectively; the ^2Π_r state is not that suggested in most recent experimental studies. All of these molecules were found to be quite strongly bound although the bond lengths, bond energies, and harmonic frequencies vary slightly among them, as a result of the nonbonding character of the 2π-MO (molecular orbital) [composed almost entirely of the Si 3p-AO (atomic orbital)], the occupation of which varies from 0 to 2 within the ^1Σ^+, ^2Π_r, and ^3Σ^− series. The neutral SiCu is found to have bound excited electronic states of ^4Σ^−, ^2Δ, ^2Σ^+, and ^2Π_i symmetry lying 0.5, 1.2, 1.8, and 3.2 eV above the ^2Π_r ground state. It is possible but not yet certain that the ^2Π_i state is, in fact, the “B state” observed in the recent experimental studies by Scherer, Paul, Collier, and Saykally

Density Functional Calculations On First-Row Transition Metals

The excitation energies and ionization potentials of the atoms in the first transition series are notoriously difficult to compute accurately. Errors in calculated excitation energies can range from 1--4 eV at the Hartree-Fock level, and errors as high as 1.5eV are encountered for ionization energies. In the current work we present and discuss the results of a systematic study of the first transition series using a spin-restricted Kohn-Sham density-functional method with the gradient-corrected functionals of Becke and Lee, Yang and Parr. Ionization energies are observed to be in good agreement with experiment, with a mean absolute error of approximately 0.15eV; these results are comparable to the most accurate calculations to date, the Quadratic Configuration Interaction (QCISD(T)) calculations of Raghavachari and Trucks. Excitation energies are calculated with a mean error of approximately 0.5eV, compared with \sim 1\mbox{eV} for the local density approximation and 0.1eV for QCISD(T). These gradient-corrected functionals appear to offer an attractive compromise between accuracy and computational effort.Comment: Journal of Chemical Physics, 29, LA-UR-93-425

A gyökfogó dokozahexaénsav mint agyvédő = Docosahexaenoic acid (DHA) as a free radical scavenger brain protector

Telítetlen zsírsavak (PUFA) fontos szerepet játszanak mint antioxidánsok az emberi testben, különös tekintettel az agyban. Lipidek szisztematikus számítási vizsgálatait az OTKA támogatás előtt már elkezdtük. A támogatás alatt 4 fő tématerületen értünk el eredményeket: Téma 1: Molekuláris konformció változások termodinamikai alapjai Egyszerű szerves molekulák, mint különböző szénhidrogén származékok, peptidek, folytonos termodinamikai fügvényeit állítottuk elő konformációs mozgások mentén. Téma 2: Zsirsavak konformációs információ Igazoltuk a PUFA-k flexibilátásbeli hasonlóságát a peptidekhez a potenciál felületek hasonlóságával. DHA a legfontosabb képviselője a PUFA családnak. Téma 3: Foszfolipidek konformációs információi Az első két téma eredmnyeinek felhasználásával egyszerű foszfolipid modelleket konstruáltunk. A két zsirsavlánc relativ helyzte, kölcsönhatásai, membránszerű elrendeződés esetén állt vizsgálataink homlokterében. Téma4 Szabadgyökök reakciói PUFA és PUFA modellekkel Szabadgyökök és reakcióik PUFA-val lipidek kettősrétegeiben biológiailag nagyon fontos folyamatok. Az E vitamin az egyik leghatékonyabb gyökfogó membránokban. A PUFA-kban mindig megtalálható allil-C-H kötések és különböző típusú gyökök reakcióinak kiterjedt vizsgálata folyt. | Polyunsaturated fatty acids (PUFA) play an important role as an antioxidant in the whole human body but more specifically in the brain. The overall project had 4 Topics: Topic 1 Fundamental Thermodynamics of Molecular Conformational Changes: Simple organic molecules were investigated in computing continues thermodynamic functions along conformational changes. These included a variety of compounds from hydrocarbons to peptides. Topic 2 Conformational information of fatty acid: Interestingly enough their felxibility was similar to that of peptides as could be judged from the similarity of their conformational potential energy surfaces. Topic 3 Conformational information of phospholipids: The results and experience obtained from the first two topics were used to construct simple phospholipids. The relative orientations of the two fatty acids in a phospholipid had to be studied to see if the nearly parallel arrangement within the lipid bilayer is enforced by nearest neighbour interaction or if such a geometry is an intrinsically stable structure. Topic 4 Free radical reactions with PUFA and PUFA models: Free radicals and their reactions with PUFA within the lipid bilayer are a biologically very important reactions. The generation of free radicals and their transformation as well as their reactions with allylic C-H bonds, which are always present is PUFA, has been studied in details

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

The weakly bound HOONO product of the OH + NO_2 + M reaction is studied using the vibrational predissociation that follows excitation of the first OH overtone (2nu1). We observe formation of both cis-cis and trans-perp conformers of HOONO. The trans-perp HOONO 2nu1 band is observed under thermal (223–238 K) conditions at 6971 cm^(–1). We assign the previously published (warmer temperature) HOONO spectrum to the 2nu1 band at 6365 cm^(–1) and 2nu1-containing combination bands of the cis-cis conformer of HOONO. The band shape of the trans-perp HOONO spectrum is in excellent agreement with the predicted rotational contour based on previous experimental and theoretical results, but the apparent origin of the cis-cis HOONO spectrum at 6365 cm^(–1) is featureless and significantly broader, suggesting more rapid intramolecular vibrational redistribution or predissociation in the latter isomer. The thermally less stable trans-perp HOONO isomerizes rapidly to cis-cis HOONO with an experimentally determined lifetime of 39 ms at 233 K at 13 hPa (in a buffer gas of predominantly Ar). The temperature dependence of the trans-perp HOONO lifetime in the range 223–238 K yields an isomerization barrier of 33±12 kJ/mol. New ab initio calculations of the structure and vibrational mode frequencies of the transition state perp-perp HOONO are performed using the coupled cluster singles and doubles with perturbative triples [CCSD(T)] model, using a correlation consistent polarized triple zeta basis set (cc-pVTZ). The energetics of cis-cis, trans-perp, and perp-perp HOONO are also calculated at this level [CCSD(T)/cc-pVTZ] and with a quadruple zeta basis set using the structure determined at the triple zeta basis set [CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ]. These calculations predict that the anti form of perp-perp HOONO has an energy of DeltaE0 = 42.4 kJ/mol above trans-perp HOONO, corresponding to an activation enthalpy of DeltaH298[double-dagger]0 = 41.1 kJ/mol. These results are in good agreement with statistical simulations based on a model developed by Golden, Barker, and Lohr. The simulated isomerization rates match the observed decay rates when modeled with a trans-perp to cis-cis HOONO isomerization barrier of 40.8 kJ/mol and a strong collision model. The quantum yield of cis-cis HOONO dissociation to OH and NO2 is also calculated as a function of photon excitation energy in the range 3500–7500 cm^(–1), assuming D0 = 83 kJ/mol. The quantum yield is predicted to vary from 0.15 to 1 over the observed spectrum at 298 K, leading to band intensities in the action spectrum that are highly temperature dependent; however, the observed relative band strengths in the cis-cis HOONO spectrum do not change substantially with temperature over the range 193–273 K. Semiempirical calculations of the oscillator strengths for 2nu1(cis-cis HOONO) and 2nu1(trans-perp HOONO) are performed using (1) a one-dimensional anharmonic model and (2) a Morse oscillator model for the OH stretch, and ab initio dipole moment functions calculated using Becke, Lee, Yang, and Parr density functional theory (B3LYP), Møller-Plesset pertubation theory truncated at the second and third order (MP2 and MP3), and quadratic configuration interaction theory using single and double excitations (QCISD). The QCISD level calculated ratio of 2nu1 oscillator strengths of trans-perp to cis-cis HOONO is 3.7:1. The observed intensities indicate that the concentration of trans-perp HOONO early in the OH + NO2 reaction is significantly greater than predicted by a Boltzmann distribution, consistent with statistical predictions of high initial yields of trans-perp HOONO from the OH + NO_2 + M reaction. In the atmosphere, trans-perp HOONO will isomerize nearly instantaneously to cis-cis HOONO. Loss of HOONO via photodissociation in the near-IR limits the lifetime of cis-cis HOONO during daylight to less than 45 h, other loss mechanisms will reduce the lifetime further