Twisting dynamics in the excited singlet state of Michler's ketone

Ultrafast relaxation dynamics of the excited singlet (S(1)) state of Michler's ketone (MK) has been investigated in different kinds of solvents using a time-resolved absorption spectroscopic technique with 120 fs time resolution. This technique reveals that conversion of the locally excited (LE) state to the twisted intramolecular charge transfer (TICT) state because of twisting of the N,N-dimethylanilino groups with respect to the central carbonyl group is the major relaxation process responsible for the multi-exponential and probe-wavelength-dependent transient absorption dynamics of the S1 state of MK, but solvation dynamics does not have a significant role in this process. Theoretical optimization of the ground-state geometry of MK shows that the dimethylanilino groups attached to the central carbonyl group are at a dihedral angle of about 51 degrees with respect to each other because of steric interaction between the phenyl rings. Following photoexcitation of MK to its S1 state, two kinds of twisting motions have been resolved. Immediately after photoexcitation, an ultrafast "anti-twisting" motion of the dimethylanilino groups brings back the pretwisted molecule to a near-planar geometry with high mesomeric interaction and intramolecular charge transfer (ICT) character. This motion is observed in all kinds of solvents. Additionally, in solvents of large polarity, the dimethylamino groups undergo further twisting to about 90 degrees with respect to the phenyl ring, to which it is attached, leading to the conversion of the ICT state to the TICT state. Similar characteristics of the absorption spectra of the TICT state and the anion radical of MK establish the nearly pure electron transfer (ET) character of the TICT state. In aprotic solvents, because of the steep slope of the potential energy surface near the Franck-Condon (FC) or LE state region, the LE state is nearly nonemissive at room temperature and fluorescence emission is observed from only the ICT and TICT states. Alternatively, in protic solvents, because of an intermolecular hydrogen-bonding interaction between MK and the solvent, the LE region is more flat and stimulated emission from this state is also observed. However, a stronger hydrogen-bonding interaction between the TICT state and the solvent as well as the closeness between the two potential energy surfaces due to the TICT and the ground states cause the nonradiative coupling between these states to be very effective and, hence, cause the TICT state to be weakly emissive. The multi-exponentiality and strong wavelength-dependence of the kinetics of the relaxation process taking place in the S1 state of MK have arisen for several reasons, such as strong overlapping of transient absorption and stimulated emission spectra of the LE, ICT, and TICT states, which are formed consecutively following photoexcitation of the molecule, as well as the fact that different probe wavelengths monitor different regions of the potential energy surface representing the twisting motion of the excited molecule.     

Nucleation efficiency of R134a as a sensitive liquid for superheated drop emulsion detector

Superheated emulsion detector is known to detect neutrons, γ-rays and other charged particles. The present work includes the study of nucleation efficiency of superheated drops of one of the CFC-free liquids, R134a (C₂H₂F₄), to fast neutrons, its response to γ-rays from ²⁴¹Am and ¹³⁷Cs and compare its nucleation efficiency with that of R12. The observation indicates that because of the presence of hydrogen, the nucleation efficiency is less in R134a than in R12 in the present neutron energy range of consideration. R134a is one of the most environment-friendly, commercially available liquid that is suitable for superheated drop detector, specially in neutron dosimetry and one needs to investigate it in detail.     

Design of medium energy beam transport line between the RFQ and the Linac in the radioactive ion beam facility at VECC,Kolkata

The design of a medium energy beam transport (MEBT) line comprising of a re-buncher and four quadrupoles, two upstream and the other two downstream of the re-buncher, has been presented. The design was done to ensure almost 100% transport of heavy-ion beams of about 99 keV/u energy from RFQ having a q/A not less than 1/14 through the re-buncher and then through IH Linac of about 0.6 m length in which beam would be accelerated to about 185 keV/u. The re-buncher has been designed to operate at 37.8 MHz, the resonating frequency of both the RFQ and the IH Linac. The entire beam line has been installed and recently O⁵⁺ beam from RFQ has been transported through the re-buncher and subsequently accelerated in the IH Linac successfully.     

On decompositions of semirings via <Emphasis Type="Italic">k</Emphasis>-radicals of some relations

We generalize the notion of k-radical of Green’s \({\overline{\mathcal{J}}}\)-relation, study the decompositions of semirings and investigate the semirings on which the powers and transitive closures of k-radicals are distributive lattice congruences.     

Problems on matchings and independent sets of a graph

Let $G$ be a finite simple graph. For $X?V\left(G\right)$, the difference of $X$, $d\left(X\right)?\left|X\right|?\left|N\left(X\right)\right|$ where $N\left(X\right)$ is the neighborhood of $X$ and $max\{d\left(X\right):X?V\left(G\right)\}$ is called the critical difference of $G$. $X$ is called a critical set if $d\left(X\right)$ equals the critical difference and $\ker \left(G\right)$ is the intersection of all critical sets. $\mathrm{diadem}\left(G\right)$ is the union of all critical independent sets. An independent set $S$ is an inclusion minimal set with$d\left(S\right)>0$ if no proper subset of $S$ has positive difference.A graph $G$ is called a König–Egerváry graph if the sum of its independence number $\alpha \left(G\right)$ and matching number $\mu \left(G\right)$ equals $\left|V\left(G\right)\right|$.In this paper, we prove a conjecture which states that for any graph the number of inclusion minimal independent set $S$ with $d\left(S\right)>0$ is at least the critical difference of the graph.We also give a new short proof of the inequality $\left|\ker \left(G\right)\right|+\left|\mathrm{diadem}\left(G\right)\right|\le 2\alpha \left(G\right)$.A characterization of unicyclic non-König–Egerváry graphs is also presented and a conjecture which states that for such a graph $G$, the critical difference equals $\alpha \left(G\right)?\mu \left(G\right)$, is proved.We also make an observation about $\ker \left(G\right)$ using Edmonds–Gallai Structure Theorem as a concluding remark.     

Wavelet variance analysis for gappy time series

The wavelet variance is a scale-based decomposition of the process variance for a time series and has been used to analyze, for example, time deviations in atomic clocks, variations in soil properties in agricultural plots, accumulation of snow fields in the polar regions and marine atmospheric boundary layer turbulence. We propose two new unbiased estimators of the wavelet variance when the observed time series is ‘gappy,’ i.e., is sampled at regular intervals, but certain observations are missing. We deduce the large sample properties of these estimators and discuss methods for determining an approximate confidence interval for the wavelet variance. We apply our proposed methodology to series of gappy observations related to atmospheric pressure data and Nile River minima.     

Femtosecond study of partially folded states of cytochrome C by solvation dynamics

Using femtosecond time-resolved fluorescence spectroscopy, it is shown that the solvation dynamics in the two partially folded states (IS' and IS' ') of a protein, cytochrome C, are very different. In the case of IS' (formed by the addition of 2 mM sodium dodecyl sulfate, SDS) almost the entire dynamic solvent shift of coumarin 153 (C153) is captured in a picosecond setup and the contribution of the ultrafast component (0.5 ps) is very small (5%). Solvation dynamics of IS' ' (formed by 2 mM SDS and 5 M urea) displays a major component (47%) of 1.3 ps. This indicates that the structure of IS' ' is much more open and exposed compared to that of IS'. The difference in the dynamics of IS' and IS' ' is attributed to differences in their structure, particularly near the heme region, and the presence of urea in IS' '.     

Facile synthesis of polyacrylate directed silver nanoparticles for pH sensing through naked eye

Poly(acrylic acid) (PAA) and its salt poly(acrylate) (PA) have been synthesized through modified free radical polymerization in environmentally begin aqueous medium under ultrasound to make the process robust. The synthesized polymer is well-characterized through conventional techniques. Its salt is employed to produce highly stable and stimuli sensitive colloidal silver (Ag-PA sol) without using any additional reducing chemical reagents like sodium borohydride, ascorbic acid, hydrazine, etc or UV/Gamma radiation. A detailed mechanistic path of the polymerization and reduction of Ag⁺ on polyacrylate chains has been evaluated. Finally Ag-PA sol is used for pH sensing through naked eye to eliminate the need for sophisticated instrument for data collection. The present work focuses mainly the development of a low cost pH sensing system based on colorimetric ‘smart polymer’ having high practical utility. The unique structural and photo-physical features of nano-scaled materials open new opportunities for the applications of colorimetric pH sensor. In the present work, Ag nano-clusters capped by PA^? are employed as an effective colorimetric pH sensor for the first time, requiring no further functionalization.     

Defect production in nonlinear quench across a quantum critical point

We show that the defect density n, for a slow nonlinear power-law quench with a rate tau(-1) and an exponent alpha>0, which takes the system through a critical point characterized by correlation length and dynamical critical exponents nu and z, scales as n approximately tau(-alphanud/(alphaznu+1)) [n approximately (alphag((alpha-1)/alpha)/tau)(nud/(znu+1))] if the quench takes the system across the critical point at time t=0 [t=t(0) not = 0], where g is a nonuniversal constant and d is the system dimension. These scaling laws constitute the first theoretical results for defect production in nonlinear quenches across quantum critical points and reproduce their well-known counterpart for a linear quench (alpha=1) as a special case. We supplement our results with numerical studies of well-known models and suggest experiments to test our theory.