A hermitian open-shell many-body perturbation theory for treating intruder states

In this paper we have formulated an open-shell many-body perturbation theory (mbpt) that applies to an incomplete model space. The effective HamiltonianH ^eff generated in our theory is hermitian. We follow the resolvent-operator based time-dependent formulation ofmbpt of Banerjeeet al, and show quite generally that, by classifying the various determinants spanning the Hilbert space as model valence spaceP, virtual valence spaceR and virtual spaceQ, a diagrammaticmbpt satisfying size consistency can be developed. The chief new features of the theory are (i) manifest hermiticity ofH ^eff; (ii) presence of disconnected diagrams no part of which is a legitimate diagram (irreducible disconnected diagrams); (iii) presence of folded diagrams with components that may be irreducible disconnected diagrams; (iv) a consistent treatment of the variousn-valence sectors of the Hilbert space that may be interacting throughH ^eft if valence-holes are present—in particular a modified treatment of the core-valence separation. The generalisation afforded by the theory offers useful conceptual as well as computational advantages because the convergence difficulty encountered in a complete valence space formulation may be bypassed here by keeping the offending valence space determinants out of the model space. A brief critique of the developmentvis-a-vis the only other general model space development leading to a nonhermitianH ^eff is also given.     

Fock space multireference coupled cluster theory: noniterative inclusion of triples for excitation energies

In this paper we propose and numerically implement a specific scheme for calculating the excitation energies (EEs) within the Fock space multireference coupled cluster framework, which includes the contributions from noniterative triples cluster amplitudes. These contribute to the EEs at the third order. We present results for CH⁺ and N2, and study the effects of these noniterative triples on EEs. Received: 28 July 1997 / Accepted: 8 December 1997     

A comparative calculation on excited state energies of some conjugated hydrocarbons

The energies of the single-configuration lowest π – π* singlet and triplet states of some conjugated hydrocarbons have been calculated by the MC-SCF method using the conjugate-gradient technique of minimisation. The results are compared with those calculated by other methods currently in use, like (a) single-configuration calculation with V_N?1 potential for virtual orbitals; (b) CI calculation involving singly excited states; and (c) TDHF method. It has been concluded that the results for the MC-SCF method are very good, considering that only a single open-shell configuration is involved.     

Quantum escape kinetics over a fluctuating barrier

The escape rate of a particle over a fluctuating barrier in a double-well potential exhibits resonance at an optimum value of correlation time of fluctuation. This has been shown to be important in several variants of kinetic model of chemical reactions. We extend the analysis of this phenomenon of resonant activation to quantum domain to show how quantization significantly enhances resonant activation at low temperature due to tunneling.     

Fluorometric study of solvation characteristics of ketocyanine dyes in mixed binary solvents

The fluorescence characteristics of two ketocyanine dyes have been studied in six mixed binary solvents. Several parameters such as the maximum energy E₁₂(F) of fluorescence, the quantum yield Φ₁₂ of fluorescence and the normalized intensity of the fluorescence have been investigated as functions of solvent composition. In protic+aprotic binary mixtures a dramatic change at the aprotic end has been observed. The results point to a preferential solvation of the solute by the protic component.     

Fluorimetric study of interaction of merbromin with trypsin

Interaction of merbromin with trypsin is of bovine origin has been studied by monitoring the absorption steady-state and time-resolved fluorescence spectral properties of the dye. Studies have been done in media of varying pH at different trypsin concentrations. It has been observed that trypsin brings about a quenching of fluorescence of the dye. The quenching is static in nature and the equilibrium constant of dye-trypsin interaction in the ground-state has been determined from quenching studies. Steady-state anisotropy of the dye increases in presence of trypsin in the medium. Values of micro-viscosity in the vicinity of the fluorophore in media containing trypsin have been determined from measurements of fluorescence anisotropy. Time-resolved fluorescence studies indicate the existence of two decaying states for the dye. The fractional contribution to the time-resolved decay changes with pH. The average lifetime, however, does not depend on the concentration of trypsin.     

Structural elucidation of a nickel boryl complex. A recyclable borylation Ni(II) reagent of bromobenzene

The first nickel complex bearing a boryl moiety, (PNP)Ni[B(catechol)](PNP = N[2-P(CHMe(2))(2)-4-methylphenyl](2)(-)), has been prepared, structurally characterized, and analyzed by DFT; this rare species is shown to be a recyclable reagent for the borylation of bromobenzene, via an unusual cycle, by applying the ingredients catecholborane and NaBH(4).