Resonance de-enhancement in the 2(1)A(g) state of trans-azobenzene

We analyze the origin of de-enhancement for a number of vibrational modes in the 2(1)A(g) excited state of trans-azobenzene. We have used the time-dependent wave packet analysis of the RR intensities by including the multimode damping effects in the calculation. This avoids the use of unrealistically large values for the damping parameter. It is concluded that the de-enhancement is caused by the interference between the two uncoupled electronic states, and that the intensities observed under the so-called symmetry forbidden 2(1)A(g) <-- 1(1)A(g) transition are purely due to resonance excitation. It is also observed that the use of the time-dependent approach to study the de-enhancement effects caused by multiple electronic states on the RR intensities is not necessarily useful if one is interested in the structural dynamics.

Structure-reactivity correlations of excited states of perfluorinated compounds: A time resolved Raman study

This paper reports the TR3 spectral studies on perfluorinated organic systems with the objective to understand the influence of perfluorination on the excited states. We have recorded the TR3 spectra and Raman excitation profiles of the triplet excited states of decafluorobenzophenone and fluoranil. It is found that the influence of perfluorination is more pronounced in the triplet excited state than the ground state and thus leads to enhanced reactivity for perfluorinated compounds through larger structural distortions.

Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites: Role of cation-guest binding

Through a systematic study of several diphenylcyclopropane derivatives, we have inferred that the cations present within a zeolite control the excited-state chemistry of these systems. In the parent 1,2-diphenylcylopropane, the cation binds to the two phenyl rings in a sandwich-type arrangement, and such a mode of binding prevents cis-to-trans isomerization. Once an ester or amide group is introduced into the system (derivatives of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid), the cation binds to the carbonyl group present in these chromophores and such a binding has no influence on the cis-trans isomerization process. Cation-reactant structures computed at density functional theory level have been very valuable in rationalizing the observed photochemical behavior of diphenylcyclopropane derivatives included in zeolites. While the parent system, 1,2-diphenyleylopropane, has been extensively investigated in the context of chiral induction in solution, owing to its failure to isomerize from cis to trans, the same could not be investigated in zeolites. However, esters of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid could be studied within zeolites in the context of chiral induction. Chiral induction as high 20% ee and 55% de has been obtained with selected systems. These numbers, although low, are much higher than what has been obtained in solution with the same system or with the parent system by other investigators (maximum similar to10% ee).

Effect of chlorine substitution on triplet state structure of thioxanthone: A time-resolved resonance Raman study

Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time-resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2-chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of 3n-pi* to 3 pi-pi* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright (C) 2013 John Wiley & Sons, Ltd.

Linear and nonlinear optical properties of expanded porphyrins: a DMRG study

We study absorption spectra and two photon absorption coefficient of expanded porphyrins (EPs) by the density matrix renormalization group (DMRG) technique. We employ the Pariser-Parr-Pople (PPP) Hamiltonian which includes long-range electron-electron interactions. We find that, in the 4n+2 EPs, there are two prominent low-lying one-photon excitations, while in 4n EPs, there is only one such excitation. We also find that 4n+2 EPs have large two-photon absorption cross sections compared to 4n EPs. The charge density rearrangement in the one-photon excited state is mostly at the pyrrole nitrogen site and at the meso carbon sites. In the two-photon states, the charge density rearrangement occurs mostly at the aza-ring sites. In the one-photon state, the C-C bond length in aza rings shows a tendency to become uniform. In the two-photon state, the bond distortions are on C-N bonds of the pyrrole ring and the adjoining C-C bonds which connect the pyrrole ring to the aza or meso carbon sites.

Efficiency limitations in a low band-gap diketopyrrolopyrrole-based polymer solar cell

We report the performance and photophysics of a low band-gap diketopyrrolopyrrole-based copolymer used in bulk heterojunction devices in combination with PC71BM. We show that the short lifetime of photogenerated excitons in the polymer constitutes an obstacle towards device efficiency by limiting the diffusion range of the exciton to the donor-acceptor heterojunction. We employ ultrafast transient-probe and fluorescence spectroscopy techniques to examine the excited state loss channels inside the devices. We use the high boiling point solvent additive 1,8-diiodooctane (DIO) to study the photoexcited state losses in different blend morphologies. The solvent additive acts as a compatibiliser between the donor and the acceptor material and leads to smaller domain sizes, higher charge formation yields and increased device efficiency.

Constraining gravity using entanglement in AdS/CFT

We investigate constraints imposed by entanglement on gravity in the context of holography. First, by demanding that relative entropy is positive and using the Ryu-Takayanagi entropy functional, we find certain constraints at a nonlinear level for the dual gravity. Second, by considering Gauss-Bonnet gravity, we show that for a class of small perturbations around the vacuum state, the positivity of the two point function of the field theory stress tensor guarantees the positivity of the relative entropy. Further, if we impose that the entangling surface closes off smoothly in the bulk interior, we find restrictions on the coupling constant in Gauss-Bonnet gravity. We also give an example of an anisotropic excited state in an unstable phase with broken conformal invariance which leads to a negative relative entropy.

Kinetically stabilized C-60-toluene solvate nanostructures with a discrete absorption edge enabling supramolecular topotactic molecular exchange

Nanosized fullerene solvates have attracted widespread research attention due to recent interesting discoveries. A particular type of solvate is limited to a fixed number of solvents and designing new solvates within the same family is a fundamental challenge. Here we demonstrate that the hexagonal closed packed (HCP) phase of C-60 solvates, formed with m-xylene, can also be stabilized using toluene. Contrary to the notion on their instability, these can be stabilized from minutes up to months by tuning the occupancy of solvent molecules. Due to high stability, we could record their absorption edge, and measure excitonic life-time, which has not been reported for any C-60 solvate. Despite being solid, absorbance spectrum of the solvates is similar in appearance to that of C-60 in solution. A new absorption band appears at 673 nm. The fluorescence lifetime at 760 nm is similar to 1.2 ns, suggesting an excited state unaffected by solvent-C-60 interaction. Finally, we utilized the unstable set of HCP solvates to exchange with a second solvent by a topotactic exchange mechanism, which rendered near permanent stability to the otherwise few minutes stable solvates. This is also the first example of topotactic exchange in supramolecular crystal, which is widely known in ionic solids. (C) 2014 Elsevier Ltd. All rights reserved.

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

Two novel triads based on a diketopyrrolopyrrole (DPP) central core and two 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) units attached by thiophene rings have been synthesised having high molar extinction coefficients. These triads were characterised and used as donor materials in small molecule, solution processable organic solar cells. Both triads were blended with PC71BM as an acceptor in different ratios by wt% and their photovoltaic properties were studied. For both the triads a modest photovoltaic performance was observed, having an efficiency of 0.65%. Moreover, in order to understand the ground and excited state properties and vertical absorption profile of DPP and BODIPY units within the triads, theoretical DFT and TDDFT calculations were performed.

Quench dynamics and parity blocking in Majorana wires

We theoretically explore quench dynamics in a finite-sized topological fermionic p-wave superconducting wire with the goal of demonstrating that topological order can have marked effects on such non-equilibrium dynamics. In the case studied here, topological order is reflected in the presence of two (nearly) isolated Majorana fermionic end bound modes together forming an electronic state that can be occupied or not, leading to two (nearly) degenerate ground states characterized by fermion parity. Our study begins with a characterization of the static properties of the finite-sized wire, including the behavior of the Majorana end modes and the form of the tunnel coupling between them; a transfer matrix approach to analytically determine the locations of the zero energy contours where this coupling vanishes; and a Pfaffian approach to map the ground state parity in the associated phase diagram. We next study the quench dynamics resulting from initializing the system in a topological ground state and then dynamically tuning one of the parameters of the Hamiltonian. For this, we develop a dynamic quantum many-body technique that invokes a Wick's theorem for Majorana fermions, vastly reducing the numerical effort given the exponentially large Hilbert space. We investigate the salient and detailed features of two dynamic quantities-the overlap between the time-evolved state and the instantaneous ground state (adiabatic fidelity) and the residual energy. When the parity of the instantaneous ground state flips successively with time, we find that the time-evolved state can dramatically switch back and forth between this state and an excited state even when the quenching is very slow, a phenomenon that we term `parity blocking'. This parity blocking becomes prominently manifest as non-analytic jumps as a function of time in both dynamic quantities.

Optical and nonlinear absorption properties of Na doped ZnO nanoparticle dispersions

We report linear and nonlinear optical properties of the biologically important Na doped ZnO nanoparticle dispersions. Interesting morphological changes involving a spherical to flowerlike transition have been observed with Na doping. Optical absorption measurements show an exciton absorption around 368 nm. Photoluminescence measurements reveal exciton recombination emission, along with shallow and deep trap emissions. The increased intensity of shallow trap emission with Na doping is attributed to oxygen deficiency and shape changes associated with doping. Nonlinear optical measurements show a predominantly two-photon induced, excited state absorption, when excited with 532 nm, 5 ns laser pulses, indicating potential optical limiting applications.

Photochemical Reactions in Oriented Systems

Modification of chemical reactions through the use of constrained and/or organized media has attracted a great deal of attention recently. Results from our laboratory in this direction which include a study of photochemical reactions in solid state and in cyclodextrins are presented here. A study of solid state photochemical behavior of coumarins has provided information regarding subtler aspects of topochemical postulates of photodimerization. Results pertaining to geometrical criteria for photodimerization and "chloro" as a crystal engineering group are discussed. As a part of an attempt to correlate chemical reactivity with molecular packing in the solid state, photooxidation of diarylthioketones in the solid state has been investigated. The observed differences in the reactivity of these crystals are rationalized in terms of crystal packing. Though cyclodextrins have been extensively studied, very few photochemical reactions involving molecules complexed to cyclodextrins have been examined. In this connection, the utility of cyclodextrins in bringing about selectivity in photochemical reactions through the study of excited state behavior of olefins and aryl alkyl ketones has been demonstrated in our laboratory.

Metal ions in molecular association of porphyrins

Molecular association of porphyrins and their metal derivatives has been recognized as one of the important properties for many of their biological functions. The association is classified into (i) self-aggregation, (ii) intermolecular association and (iii) intramolecular association. The presence of metal ions in the porphyrin cavity is shown to alter the magnitudes of binding constants and thermodynamic parameters of complexation. The interaction between the porphyrin unit and the acceptor is described in terms of π-π interaction. The manifestation of charge transfer states both in the ground and excited states of these complexes is shown to influence the rates of excited state electron transfer reactions. Owing to paucity of crystal structure data, the time-averaged geometries of many of these complexes have been derived from magnetic resonance data.

A study of interaction in the lowest singlet and triplet states of H2

The potential energy curves of the ground state and the first excited state of H2 are examined in terms of the electronic force acting on each nucleus. The results reveal the detailed course of events that occur when two hydrogen atoms with parallel and antiparallel electron spins approach one another from a large internuclear separation.

Understanding solvent effects on structure and reactivity of organic intermediates: a Raman study

The effect of solvent on chemical reactivity has generally been explained on the basis of the dielectric constant and viscosity. However a number of spectroscopic studies, including UV-VIS, IR and Raman, has led to numerous empirical parameters to define solvent effect based on either solvating ability or polarity scale. These parameters include solvent polarizability, dipolarity, Lewis acidity and Lewis basicity, E-T(30), pi*, alpha, beta etc. However, from a structural point of view, we can separate solvation as static and dynamic processes. The static solvation basically relates to stabilization of the molecular structure by the solvent to attain the equilibrium structure, both in the intermediate and ground state. Dynamic solvation relates to solvent reorganization-induced dynamics prior to the structural reorganization to reach the equilibrium state. In this paper, we present (a) structural distortions induced by the solvent due to preferential solvation of the triplet excited state, and (b) the importance of dynamic solvation induced by vibronic coupling (pseudo-Jahn-Teller coupling). The examples include the effect of solvent on structure and reactivity of excited states of 2,2,2-trifluoroacetophenone (TFA). Based on the comparison of time resolved resonance Raman (TR3) data of TFA and other substituted acetophenone systems, it was found that change in solvent polarity indeed results in electronic state switching and structural changes in the excited state, which explains the trend in reactivity. Further, a TR3 study of fluoranil (FA) in the triplet excited state in solvents of varying polarities indicates that the structure of FA in the triplet excited state is determined by vibronic coupling effects and thus distorted structure. These experimental results have been well supported by density functional theoretical computational studies.