Chemisorption of atomic aluminum on Si(111): Evidence for an adsorbate-induced relaxation based on ab initio cluster-model calculations

Interaction models of atomic Al with Si4H9, Si4H7, and Si6H9 clusters have been studied to simulate Al chemisorption on the Si(111) surface in the atop, fourfold atop, and open sites. Calculations were carried out using nonempirical pseudopotentials in the framework of the ab initio Hartree-Fock procedure. Equilibrium bond distances, binding energies for adsorption, and vibrational frequencies of the adatoms are calculated. Several basis sets were used in order to show the importance of polarization effects, especially in the binding energies. Final results show the importance of considering adatom-induced relaxation effects to specify the order of energy stabilities for the three different sites, the fourfold atop site being the preferred one, in agreement with experimental findings.

Ab initio cluster-model study of the on-top chemisorption of F and Cl on Si(111) and Ge(111) surfaces

The interaction of atomic F and Cl with Si4H9 and Ge4H9 cluster models has been studied by using ab initio pseudopotentials and basis sets of increasing complexity. The results show that the effect of d orbitals is important in order to reproduce the experimental findings. However, the use of polarization functions in the atoms which are directly involved in the chemisorption bond leads to results which are very close to those obtained using extended basis sets. The local nature of the chemisorption bond is also interpreted by means of a Mulliken population analysis. For F-Si4H9 and Cl-Si4H9 the present results are in good agreement with previous ab initio all-electron calculations, and for the chemisorption of Cl on Si(111) and Ge(111) surfaces, good agreement is found with respect to the available experimental results as well as with previous slab calculations based on the local-density-functional formalism.

Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

Single spin-echo T 2 relaxation times of cerebral metabolites at 14.1 T in the in vivo rat brain.

OBJECT: To determine the single spin-echo T 2 relaxation times of uncoupled and J-coupled metabolites in rat brain in vivo at 14.1 T and to compare these results with those previously obtained at 9.4 T. MATERIALS AND METHODS: Measurements were performed on five rats at 14.1 T using the SPECIAL sequence and TE-specific basis-sets for LCModel analysis. RESULTS AND CONCLUSION: The T 2 of singlets ranged from 98 to 148 ms and T 2 of J-coupled metabolites ranged from 72 ms (glutamate) to 97 ms (myo-inositol). When comparing the T 2s of the metabolites measured at 14.1 T with those previously measured at 9.4 T, a decreasing trend was found (p < 0.0001). We conclude that the modest shortening of T 2 at 14.1 T has a negligible impact on the sensitivity of the (1)H MRS when performed at TE shorter than 10 ms.

The ESRg matrix for strong field d5 systems

This review has tried to collect and correlate all the various equations for the g matrix of strong field d5 systems obtained from different basis sets using full electron and hole formalism calculations. It has corrected mistakes found in the literature and shown how the failure to properly take in symmetry boundary conditions has produced a variety of apparently inconsistent equations in the literature. The review has reexamined the problem of spin-orbit interaction with excited t4e states and finds that the earlier reports that it is zero in octahedral symmetry is not correct. It has shown how redefining what x, y, and z are in the principal coordinate system simplifies, compared to previous methods, the analysis of experimental g values with the equations.

Modelo teórico quântico para o processo de adsorção física

This article introduces a simplified model for the theoretical study of the physical adsorption process of gaseous He on the planes (100) and (111) of the solid Xe matrix, whose crystalline structure is face centered cubic (fcc). The Ab initio calculations were carried out at the MP2 level of theory employing basis sets obtained through the Generator Coordinate Method, where the core electrons were represented by a pseudopotential. The calculated adsorption energies for the (100) and (111) faces are 5,39 and 4,18 kJ/mol, respectively. This simplified model is expected to be suitable for treating complex systems of applied interest.

Cálculos teóricos de afinidades por próton de n-alquilaminas usando o método ONIOM

The ONIOM method was used to calculate the proton affinities (PA) of n-alkylamines (CnH2n+1NH2, n = 3 to 6, 8, 10, 12, 14, 16 and 18). The calculations were carried out at several levels (HF, MP2, B3LYP, QCISD(T), ...) using Pople basis sets and at the QCISD(T) level using basis sets developed by the generator coordinate method (GCM) and adapted to effective core potentials. PAs were also obtained through the GCM and high level methods, like ONIOM[QCISD(T)/6-31+G(2df,p):MP2/6-31G+G(d,p))//ONIOM[MP2/6-31+G(d,p):HF/6-31G]. The average error using the GCM, with respect to experimental data, was 3.4 kJ mol-1.

Validação computacional de métodos compostos no estudo de propriedades moleculares

Composite methods using ONIOM and different basis sets have been used to calculate proton and electron affinities for a set of alcohols at QCISD(T)/6-311++G(2df,p) level of theory. The study was carried out considering HF, MP2 and DFT (25 exchange correlation functional) methods. The calculation performed at ONIOM2(QCISD(T)/6-311++G(2df,p):HF/6-31G(d))//ONIOM2(O3LYP/6-31G(d):HF/6-31G(d)) resulted in the smallest average absolute deviation for AP and AE, 4,75 kJ/mol e 0,43 eV, respectively.

Optimization of trial wave functions for use in quantum Monte Carlo with application to LiH

Methods for both partial and full optimization of wavefunction parameters are explored, and these are applied to the LiH molecule. A partial optimization can be easily performed with little difficulty. But to perform a full optimization we must avoid a wrong minimum, and deal with linear-dependency, time step-dependency and ensemble-dependency problems. Five basis sets are examined. The optimized wavefunction with a 3-function set gives a variational energy of -7.998 + 0.005 a.u., which is comparable to that (-7.990 + 0.003) 1 of Reynold's unoptimized \fin ( a double-~ set of eight functions). The optimized wavefunction with a double~ plus 3dz2 set gives ari energy of -8.052 + 0.003 a.u., which is comparable with the fixed-node energy (-8.059 + 0.004)1 of the \fin. The optimized double-~ function itself gives an energy of -8.049 + 0.002 a.u. Each number above was obtained on a Bourrghs 7900 mainframe computer with 14 -15 hrs CPU time.

Systematic construction of models for the exchange hole of density functional theory.

Dans ce travail, nous étendons le nombre de conditions physiques actuellement con- nues du trou d’échange exact avec la dérivation de l’expansion de quatrième ordre du trou d’échange sphérique moyenne exacte. Nous comparons les expansions de deux- ième et de quatrième ordre avec le trou d’échange exact pour des systèmes atomiques et moléculaires. Nous avons constaté que, en général, l’expansion du quatrième ordre reproduit plus fidèlement le trou d’échange exact pour les petites valeurs de la distance interélectronique. Nous démontrons que les ensembles de base de type gaussiennes ont une influence significative sur les termes de cette nouvelle condition, en étudiant com- ment les oscillations causées par ces ensembles de bases affectent son premier terme. Aussi, nous proposons quatre modèles de trous d’échange analytiques auxquels nous imposons toutes les conditions actuellement connues du trou d’échange exact et la nou- velle présentée dans ce travail. Nous évaluons la performance des modèles en calculant des énergies d’échange et ses contributions à des énergies d’atomisation. On constate que les oscillations causeés par les bases de type gaussiennes peuvent compromettre la précision et la solution des modèles.

Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

Computation of relativistic symmetry orbitals for finite double point groups

A program is presented for the construction of relativistic symmetry-adapted molecular basis functions. It is applicable to 36 finite double point groups. The algorithm, based on the projection operator method, automatically generates linearly independent basis sets. Time reversal invariance is included in the program, leading to additional selection rules in the non-relativistic limit.

Selected configuration interaction with truncation energy error and application to the Ne atom

Selected configuration interaction (SCI) for atomic and molecular electronic structure calculations is reformulated in a general framework encompassing all CI methods. The linked cluster expansion is used as an intermediate device to approximate CI coefficients BK of disconnected configurations (those that can be expressed as products of combinations of singly and doubly excited ones) in terms of CI coefficients of lower-excited configurations where each K is a linear combination of configuration-state-functions (CSFs) over all degenerate elements of K. Disconnected configurations up to sextuply excited ones are selected by Brown's energy formula, ΔEK=(E-HKK)BK2/(1-BK2), with BK determined from coefficients of singly and doubly excited configurations. The truncation energy error from disconnected configurations, Δdis, is approximated by the sum of ΔEKS of all discarded Ks. The remaining (connected) configurations are selected by thresholds based on natural orbital concepts. Given a model CI space M, a usual upper bound ES is computed by CI in a selected space S, and EM=E S+ΔEdis+δE, where δE is a residual error which can be calculated by well-defined sensitivity analyses. An SCI calculation on Ne ground state featuring 1077 orbitals is presented. Convergence to within near spectroscopic accuracy (0.5 cm-1) is achieved in a model space M of 1.4× 109 CSFs (1.1 × 1012 determinants) containing up to quadruply excited CSFs. Accurate energy contributions of quintuples and sextuples in a model space of 6.5 × 1012 CSFs are obtained. The impact of SCI on various orbital methods is discussed. Since ΔEdis can readily be calculated for very large basis sets without the need of a CI calculation, it can be used to estimate the orbital basis incompleteness error. A method for precise and efficient evaluation of ES is taken up in a companion paper

Effective atomic orbitals for fuzzy atoms

The method of extracting effective atomic orbitals and effective minimal basis sets from molecular wave function characterizing the state of an atom in a molecule is developed in the framework of the "fuzzy" atoms. In all cases studied, there were as many effective orbitals that have considerable occupation numbers as orbitals in the classical minimal basis. That is considered to be of high conceptual importance

Estimates of electronic coupling for excess electron transfer in DNA

Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a π stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31 G* and extended 6-31++ G* basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack