Search of truncation of (N−1) electron basis containing full connected triple excitations in computing main and satellite ionization potentials via Fock‐space coupled cluster approach

A valence‐universal multireference coupled cluster (VUMRCC) theory, realized via the eigenvalue independent partitioning (EIP) route, has been implemented with full inclusion of triples excitations for computing and analyzing the entire main and several satellite peaks in the ionization potential spectra of several molecules. The EIP‐VUMRCC method, unlike the traditional VUMRCC theory, allows divergence‐free homing‐in to satellite roots which would otherwise have been plagued by intruders, and is thus numerically more robust to obtain more efficient and dependable computational schemes allowing more extensive use of the approach. The computed ionization potentials (IPs) as a result of truncation of the (N−1) electron basis manifold involving virtual functions such as 2h‐p and 3h‐2p by different energy thresholds varying from 5 to 15 a.u. with 1 a.u. intervals as well as thresholds such as 20, 25, and 30 a.u. have been carefully looked into. Cutoff at around 25 a.u. turns out to be an optimal threshold. Molecules such as C₂H₄ and C₂H₂ (X = D,T), and N₂ and CO (X = D,T,Q) with Dunning's cc‐pVXZ bases have been investigated to determine all main and 2h‐p shake‐up and 3h‐2p double shake‐up satellite IPs. We believe that the present work will pave the way to a wider application of the method by providing main and satellite IPs for some problematic N‐electron closed shell systems. © 2013 Wiley Periodicals, Inc.     

Regioselective Synthesis of Benzofuran‐Annulated Six‐Membered Sulfur Heterocycles by Aryl Radical Cyclization

The tin hydride–mediated cyclization of a number of sulfides and sulfones under mild and neutral conditions has been investigated. The sulfides were in turn derived from 3(2H) benzothiofuranone and 2‐bromobenzyl bromides by phase‐transfer‐catalyzed reaction, and the corresponding sulfones were prepared by treatment of the corresponding sulfides with m‐CPBA at room temperature. The sulfides and sulfones were then reacted with ⁿ Bu₃SnH‐AIBN to afford regioselectively benzofuran‐annulated six‐membered sulfur heterocycles.     

Low-Valent Titanium Mediated Deprotection of N-Allyl/Benzyl Amines: A New Approach

A novel low-valent titanium (LVT) mediated cleavage of N-allyl/benzyl amines is reported. Regio- and chemo-selective cleavages were also observed.     

Role of solvent in the compatibility of a vinylchloride–vinylacetate–maleic acid terpolymer and nitrocellulose blends

The compatibility of cast films of a vinylchloride–vinylacetate–maleic acid terpolymer (VMCH) and nitrocellulose (NC) blends is influenced by solvents. Transparent films of VMCH/NC blends are obtained when cast from solvents such as tetrahydrofuran or cyclohexanone, whereas hazy films are obtained when cast from solvents such as acetone or ethylacetate. Visible spectroscopy and phase morphology were used to analyse the compatibility–incompatibility of the blend. Differential scanning calorimetry (DSC) studies demonstrate that the transparent film is compatible, but the hazy film is incompatible. Fourier transform infra-red (FTIR) studies establish that a greater interaction is observed between the polymer pair in case of the compatible blend than in the case of the incompatible blend. A solvent dependency of blend compatibility is reflected in this study. The conformational state of the polymers in solution, which is responsible for the compatibility phenomena, may depend on the donor number and/or Taft-β value of the solvent. The greater the donor number and/or the Taft-β value, the higher may be the level of interaction between the solvent and the polymer molecules, which in turn may give a compatible blend after removal of the solvent.     

A facile and versatile protocol for the one-pot PhI(OAc)2 mediated divergent synthesis of quinazolines from 2-aminobenzylamine

In this present work iodobenzenediacetate (PIDA) has been found to be the key reagent in absence or presence of catalytic amount of molecular iodine (I₂)/zinc chloride (ZnCl₂) to construct quinazoline scaffold from 2-aminobenzylamine and a variety of easily available aldehydes, aryl and aliphatic amines, aliphatic and aryl alcohols and nitriles. This protocol provides mild and robust conditions along with great versatility to synthesize 2-substituted quinazolines from diverse starting materials in good to excellent yields. The developed protocol is also well applicable to reactants containing ease to oxidation prone functional groups.     

Photoluminescence of 2-(2′-hydroxy-5′-methylbenzoyl)-1,5-diphenylpyrrole in aqueous and β-cyclodextrin environments: manifestation of open and closed conformers

Steady-state fluorometric studies have been performed on 2-(2′-hydroxy-5′-methylbenzoyl)-1,5-diphenylpyrrole (HMBDPP) in aqueous and aqueous β-cyclodextrin (β-CD) environments at ambient temperature. The fluorophore mostly shows a single emission in aqueous solution. Addition of β-CD to the aqueous solution of the fluorophore results in the development of another emission band at higher energy. The difference in the fluorometric behaviour is assigned to a remarkable change in the polarity of the microenvironment within the supramolecular structural environment compared to that of the bulk aqueous phase. Semi-empirical calculation (AM1-SCI) rules out the possibility of intramolecular proton transfer reaction in any of the S₀, S₁ and T₁ states of the fluorophore. It is proposed that HMBDPP exists mostly in the intermolecularly hydrogen-bonded form (open conformer) in aqueous solution while within β-CD environment, it is the intramolecularly hydrogen-bonded form (closed conformer) that predominates.     

Applicability and effectiveness of classifications models for achieving the twin objectives of growth and outreach of microfinance institutions

Measuring performance of microfinance institutions (MFIs) is challenging as MFIs must achieve the twin objectives of outreach and sustainability. We propose a new measure to capture the performance of MFIs by placing their twin achievements in a 2 × 2 grid of a classification matrix. To make a dichotomous classification, MFIs that meet both their twin objectives are classified as ‘1’ and MFIs who could not meet their dual objectives simultaneously are designated as ‘0’. Six classifiers are applied to analyze the operating and financial characteristics of MFIs that can offer a predictive modeling solution in achieving their objectives and the results of the classifiers are comprehended using technique for order preference by similarity to ideal solution to identify an appropriate classifier based on ranking of measures of performance. Out of six classifiers applied in the study, kernel lab-support vector machines achieved highest accuracy and lowest classification error rate that discriminates the best achievement of the MFIs’ twin objective. MFIs can use both these steps to identify whether they are on the right path to attaining their multiple objectives from their operating characteristics.     

A Stochastic Analysis of a Staffing Problem

Consider an organization with several categories of staff, each having a specified number of members. The age of entry into service and the age of retirement are both specified. Withdrawals occur at time-independent rates. Under this set-up, the authors have computed the maximum ages at which promotions should take place, assuming that the staff members continuing at various ages are random. Some illustrative calculations have been carried out.