Comparison of MBPT and coupled-cluster methods with full CI. Importance of triplet excitation and infinite summations

Results from full fourth-order perturbation theory [SDTQ MBPT(4)], and the coupled-cluster single- and double-excitation model (CCSD). are compared with recent full CI results for BH, HF, NH₃, and H₂O. For H₂O, studies include large symmetric displacements of the OH bonds, which offer a severe test for any single-reference MBPT/CC method. In every case. CCSD plus fourth-order triple-excitation terms provide agreement with the full CI to < 2 kcal/mole. SDTQ MBPT(4) has an error 10 kcal/mole for displaced H₂O.     

The basis set superposition error in multilevel methods: a test on the H2O and HF dimer

The basis set superposition error (BSSE) is often very important in the accurate calculation of dimerization energies. Accurate prediction of thermochemical properties requires appropriate consideration of the basis set incompleteness error. Multilevel methods introduce adjustable parameters to reproduce experimental data, that is, the higher level correction (HLC) in G3 and adjustable coefficients in the MCCM. However, the HLC term is cancelled out and the adjustable coefficients in the MCCM do not remove the BSSE completely. We have calculated the BSSE involved in the multilevel methods. The H₂O and HF dimer systems were used as a test case. This study shows that empirical coefficients do reduce the BSSE in some cases and an MCCM with good parameters can be used to reproduce dimerization energies within chemical accuracy without the BSSE correction.     

MBPT studies of van der Waals molecules. III. The reliability of apparently accurate calculations for the magnesium dimer

The interaction potential for the magnesium dimer is calculated by using the diagrammatic many-body perturbation theory within the framework of the supermolecule approach. Different approximations for the perturbation treatment of the electron correlation effects are analysed with particular emphasis on the results of the complete fourth-order many-body perturbation theory. The influence of the composition of the basis set on the calculated interaction potentials and the basis set superposition effects are investigated. It is concluded that the interaction potentials for van der Waals systems calculated by the supermolecule technique might be highly uncertain because of the basis set superposition effects at the correlated level. The advantages and disadvantages of different methods for the calculation of the energy of weakly interacting systems are discussed in the light of their ability to cope with both the electron correlation problem and the basis set superposition effect.     

Application of graphical methods of spin algebras to limited CI approaches. I. Closed shell case

The time independent diagrammatic technique based on the mathematical methods of quantum electrodynamics (second quantization, Wick's theorem, Feynman-like diagrams) is combined with graphical techniques of spin algebras to derive general expressions for the matrix elements of spin independent one- and two-particle operators between spin symmetry adapted ground, mono- and bi-excited configurations of a closed shell system. Two coupling schemes are considered for bi-excited states and their relative merits are discussed. Finally, the results are used to derive compact expressions for the coupling coefficients of the direct configuration interaction from molecular integrals (CIMI ) method.     

Generic implementation of semi-analytical CI gradients for NDDO-type methods

Generic semi-analytical energy gradients are derived and implemented for NDDO-type methods, by using numerical integral and Fock matrix derivatives in the context of an otherwise analytical approach for configuration interaction (CI) and other non-variational treatments. The correctness, numerical precision, and performance of this hybrid approach are established through comparisons with fully numerical and fully analytical calculations. The semi-analytical evaluation of the CI gradient is generally much faster than the fully numerical computation, but somewhat slower than a fully analytical calculation, which however shows the same scaling behavior. It is the method of choice whenever a fully analytical CI gradient is not available due to the lack of analytical integral derivatives. The implementation is generic in the sense that it can easily be extended to any new NDDO-type Hamiltonian. The present development of a semi-analytical CI gradient will facilitate studies of electronically excited states with recently proposed NDDO methods that include orthogonalization corrections. Dedicated to Professor Karl Jug on the occasion of his 65th birthday     

Numerical studies for a theoretical analysis of semiempirical LCAO–CI methods

A numerical investigation of Del Re and Parr's formulas [1] for the treatment of π systems has been preformed in the case of five-membered rings, using two different expressions for the core Hamiltonian and different values for the effective charges. The results obtained are discussed by analysing the three stages of the calculation: (a) a non-iterative LCAO –MO calculation; (b) the same calculation with corrections for exchange and repulsion terms arising from fluctuations of the orbital populations; (c) configuration interaction. The calculations are interesting also because they do not involve the zero differential overlap approximation; a calculation without inclusion of overlap hse been carried out for pyrrole and the results have been compared with those including S . The main conclusions hold also for σ electrons, and can serve to assess better the validity of simple σ calculations.     

Ab initio CI study of the nitric oxide dimer (N2O2)

Configuration interaction (CI) studies of the ground and electronically excited states are reported for nitric oxide dimer (N₂O₂) in itscis equilibrium geometry. The lowest triplet state (³ B ₂) is found to lie only 0.43 eV above the ground state (¹ A ₁). The¹ A ₁ ¹ B ₁ transition is shown to be responsible for the rising absorption in the near infrared region observed experimentally. The transition of¹ A ₁¹ A ₂ calculated in the visible spectrum range of 701 nm (1.77 eV) is symmetry forbidden.     

Application of graphical methods of spin algebras to limited CI approaches. II. A simple open shell case

A time independent diagrammatic technique based on the Wick theorem and graphical methods of spin algebras, as outlined in Part I, is applied to a simple open shell case having one unpaired electron in addition to the pure singlet closed shell. Compact explicit expressions for the matrix elements of a spin independent Hamiltonian between conveniently chosen spin symmetry adapted states are given for the ground, mono- and bi-excited configurations.     

New whole blood methods and instruments: glucose measurement and test menus for critical care.

A glucose oxidase-H 2O 2 substrate-selective electrode (SSE) along with eight other electrodes allows the Stat Profile 5 (SP5) to measure glucose, electrolytes, blood gases, pH, and hematocrit simultaneously in whole blood. For heparinized blood gas syringe samples (n=178), orthogonal (Deming) regression showed y=0.43 + 1.00x (mmol/L), where y is whole blood glucose, and x is plasma glucose measured with the Ektachem 400 glucose oxidase slide method. For heparinized plasma (n=197), y=0.25 + 1.02x. Least squares linear regression showed y=0.25 + 1.00x (s yxx=0.49) for whole blood versus plasma, y = 0.30 + 1.01x (s yxx=0.49) for plasma versus plasma, and r=0.994 for both cases. Whole blood and plasma glucose in the same samples measured by SSE differed by less than 1%. The SP5 combines the largest number of whole blood tests currently available in a rapid response instrument well-suited for care of the critically ill patient.     

Mono- and bichromatic electron dynamics: LiH, a test case

This paper describes an electron dynamics method where the time dependence of an external oscillating electric field is the perturbing part of the Hamiltonian. Application of the electric field induces charge movement inside the molecule and electronic transitions between the molecular orbitals. The test system is the neutral LiH molecule. The method is applied to wave functions calculated using the B3LYP (hybrid) density functional, with the STO-3G and the 6-31+G basis sets. The molecule undergoes full population inversion between the HOMO and the LUMO when the electric field is in resonance with the HOMO-LUMO energy gap. The magnitude of the electric field directly affects the rate at which electronic transitions occur and the rate at which charges move between lithium and hydrogen atoms. The method is used to model both monochromatic and bichromatic multiphoton effects in LiH. Monochromatic one-, two- and three-photon transitions occur between the HOMO, LUMO and two other virtual orbitals. There is evidence of both [1+2] direct and [1+1+1] stepwise multiphoton transitions. Bichromatically, two "laser" pulses are applied at different frequencies. Electronic transitions can be fine-tuned to occur via pre-specified pathways of virtual molecular orbitals.     

Monte Carlo simulation of vapor-liquid equilibrium and critical asymmetry of square-well dimer fluid

The critical behavior of square-well dimer fluid has been investigated using grand canonical ensemble Monte Carlo simulations combined with a histogram reweighting technique, hyper-parallel tempering and finite-size scaling. The critical temperature and density obtained are T(c)*=1.5495±0.0009 and ρ(c)*=0.1473±0.0007, which are 2.5% lower and 5.2% higher than previous results. Coexistence curves both near to and far from the critical point were obtained. The vapor-liquid equilibrium data far from the critical point are consistent with previous results. Simulation results show that the contribution of |t|(1-α) to the coexistence diameter of square-well dimer fluid dominates the critical behavior and the contribution of |t|(2β) is larger than for a hard-core square-well fluid.     

Electronic states of the benzene dimer: a simple case of complexity

Electronic structure calculations of the excited states of the benzene dimer using equation-of-motion coupled-cluster method are reported. The calculations reveal large density of electronic states, including multiple valence, Rydberg, and mixed Rydberg-valence states. The calculations of the oscillator strengths for the transitions between the excimer state (i.e., the lowest excited state of the dimer, 1(1)B(1g)) and other excited states allowed us to identify the target state responsible for the excimer absorption as the E(1u) state of a mixed Rydberg-valence character at 3.04 eV above the excimer (1(1)B(1g)). Although at D(6h) the 1(1)B(1g) → E(1u) transition is symmetry-forbidden, small geometric displacements (to D(2h)) that have a negligible effect on the excitation energy split this degenerate state into the dark (4B(3u)) and bright (4B(2u)) components (oscillator strength of 0.3 au). The excitation energy for this transition depends strongly on the dimer structure, which explains the broad character of the experimentally observed excimer absorption spectrum.     

Determination of arsenic species: a critical review of methods and applications, 2000-2003

We review recent research in the field of arsenic speciation analysis with the emphasis on significant advances, novel applications and current uncertainties.     

Electronic structure of titanium monoxide by the Xα-SW and CI methods

Parallel calculations of the spectrum of the low-lying electronic states of the TiO molecule have been performed by the nonempirical configuration-interaction method and the SCF-X method. The calculations were performed for the experimental value of the equilibrium internuclear distance in the ground electronic state. The electronic spectrum has been assigned on the basis of the results obtained, and the existence of a low-lying state of ³- symmetry has been confirmed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vo. 24, No. 2, pp. 212–215, March–April, 1988.     

Steric effect in biphenyl according to SC LCAO MO and limited CI methods

The conformation of an isolated biphenyl molecule has been analyzed with the use of a combination of theCoulson andSenent and the SC LCAO MO methods. The predicted angle between the planes of the two benzene rings and all the predicted bond lengths are in very good agreement with experiment. Using the SC LCAO MO and limited CI methods the electronic spectrum has been reinterpreted; it has been shown that the recent interpretations given byGondo and independently byGrinter need a few corrections.

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Zusammenfassung Die Konformation des isolierten Biphenyls wurde mit Hilfe einer Kombination der Coulson-Senent- und der SC-LCAO-MO-Methode analysiert. Der berechnete Winkel zwischen den Benzolebenen und alle berechneten Bindungslängen stimmen sehr gut mit dem Experiment überein. Mit Hilfe der SC-LCAO-MO und der beschränkten CI-Methode wurde auch das Spektrum neuinterpretiert; es wurde gezeigt, daß die Interpretationen, die vonGondo undGrinter gegeben wurden, zum Teil korrigiert werden müssen.

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Résumé La conformation d'une molécule isolée de biphényle a été analysée à l'aide d'une combinaison des méthodes de Coulson-Senent et des orbitales moléculaires SCF LCAO. L'angle prévu entre les plans des deux cycles benzéniques et toutes les longueurs de liaisons prédites sont en très bon accord avec l'expérience. En utilisant les méthodes SCF LCAO MO et IC limitée, le spectre électronique a été réinterprété; nous avons montré que les interprétations récentes données parGondo et indépendamment parGrinter nécessitent quelques modifications.

     

Synthesis, characterization and molecular recognition of a bis-platinum terpyridine dimer

A novel bis-platinum(II) terpyridine-based macrocycle has been quantitatively obtained by self-assembly; the Pt(II) host binds neutral planar and electron-rich aromatic guests with good selectivity in DMSO.     

Development, validation and data quality assurance of screening methods: a case study

Despite the growing importance of qualitative screening tests in routine laboratories involved in the EU official control, their validation is not as deeply explained in Commission Decision 2002/657/EC as the validation of quantitative confirmatory methods. At the same time, the issue of quality assurance of screening assays defining internal quality control (IQC) procedures as required by accreditation bodies is undoubtedly less developed in this analytical field. As an example the present study describes the development, the validation and the IQC implemented for a commercial enzyme linked immunosorbent assay (ELISA) able to detect 17-α-19-nortestosterone (α-NT) and 17-β-19-nortestosterone (β-NT) isomers in bullock urine. In order to select a suitable sample treatment, two SPE purification protocols were preliminary compared. The chosen method was therefore fully validated determining the mandatory parameters required by Commission Decision 2002/657/EC: specificity, detection capability and robustness. An in-depth discussion was carried out illustrating the possible validation approaches and their implications especially in the assessment of the key performance characteristic: detection capability. Finally, the control charts implemented for continuous method verification during analyses of real samples were reported.