Green synthesis of an ionic porous organic polymer for efficient capture of environmentally toxic MnO4- and I3- from water.

The syntheses of ionic porous organic polymers (iPOPs) via an ionothermal strategy or using solvents with high boiling points are not environmentally friendly approaches. Furthermore, green synthesis of an ionic porous organic polymer has not been reported to date. The azo-coupling reaction is considered a green synthetic strategy and has been used to obtain a new ionic porous organic polymer (iPOP-6) wherein water is used as a solvent. iPOP-6 turns out to be a useful adsorbent that can scavenge toxic water pollutants (MnO4- and I3-) in an energy efficient manner via an ion exchange based adsorption process. The distribution coefficients (Kd) associated with the removal of MnO4- and I3- are greater than 105 mL g-1 - a desirable feature observed in a superior adsorbent. iPOP-6 can remove such pollutants from water samples collected from different water bodies with good capture efficiency. The removal mechanism was also ratified by theoretical studies. Overall, this work presents a new ionic POP with improved features and performance for water purification applications.

An unbiased confirmation of the participating isomers of C2B5- in the formation of its photo-detachment spectra: a theoretical study.

The primary goal of the present article is to provide an unbiased structural confirmation of C2B5-, relying on its available experimental photo-detachment spectra. The study is performed from scratch by optimizing the lowest energy isomers of C2B5- and later, suitable molecular vibronic Hamiltonians are constructed by analyzing the normal modes of these optimized isomers. The Hamiltonians' parameters are evaluated from the fits of the calculated ab initio single point energies using a state of the art multireference configuration (MRCI) level of theory employing a correlation consistent polarized triple zeta (cc-pVTZ) basis set. The state-averaged variant of the MRCI level of theory is also applied to deal with the highly interactive electronic states of both of the isomers. A detailed analysis of the potential energy curves along the totally symmetric vibrational modes is performed to understand the energy modulation between the different electronic states and also to find the energetic locations of the conical intersections. The introduction of the non-symmetric vibrational modes in the Hamiltonians help to understand the impact of non-adiabaticity during energy modulation in the coupled surfaces. Later, both adiabatic and non-adiabatic nuclear dynamics are performed on the electronic states of both of the isomers using the constructed reduced and full-dimensional Hamiltonians. The results of the adiabatic dynamics are used to assign the positions of the simulated photo-detachment bands, while the non-adiabatic dynamics improve the shape of those bands. Finally, we compare our theoretical findings with the available experimental photo-detachment spectra of C2B5- to provide an unbiased structural confirmation of the participating isomers of C2B5- in its photo-detachment spectra.

Effect of Reagent Vibration and Rotation on the State-to-State Dynamics of the Hydrogen Exchange Reaction, H + H2 → H2 + H.

State-to-state dynamics of the benchmark hydrogen exchange reaction H + H2 (v = 0-4, j = 0-3) → H2 (v', j') + H is investigated with the aid of the real wave packet approach of Gray and Balint-Kurti (J. Chem. Phys. 1998, 108, 950-962) and electronic ground BKMP2 potential energy surface of Boothroyd et al. (J. Chem. Phys. 1996, 104, 7139-7152). Initial state-selected and product state-resolved reaction probabilities, integral cross section, and product diatom vibrational and rotational level populations at a few collision energies are reported to elucidate the energy disposal mechanism. State-specific thermal rate constants are also calculated and compared with the available literature results. Coriolis coupling terms of the nuclear Hamiltonian are included, and calculations are parallelized over the helicity quantum number, Ω'. Attempts are made, in particular, to study the effect of reagent vibrational and rotational excitations on the dynamical attributes. It is found that the calculations become computationally expensive with reagent vibrational and rotational excitation. Reagent vibrational excitation is found to enhance the reactivity and has significant impact on the energy disposal to the vibrational and rotational degrees of freedom of the product. The interplay of reagent translational and vibrational energy on the product vibrational distribution unfolds an important aspect of the energy disposal mechanism. The effect of reagent rotation on the state-to-state dynamics is found not to be very significant, and the weak effect turns out to be specific to v'.

Rationalization of photo-detachment spectra of the indenyl anion (C9H7-) from the perspective of vibronic coupling theory.

The nuclear dynamics of the low-lying first four electronic states of the prototypical indenyl radical is investigated based on first principles calculations to rationalize the experimental vibronic structure of the radical. The study is performed following both time-dependent and time-independent quantum-chemistry approaches using a model diabatic Hamiltonian. The construction of model Hamiltonians is based on the fits of the adiabatic energies calculated from the electronic structure method. The analyses of the static and dynamics results of the present study corroborate the experimental findings regarding the shape of the spectrum, vibrational progressions and the lifetime of the excited state. Finally, the present theoretical investigations suggest that the electronic non-adiabatic effect is extremely important for a detailed study of the vibronic structure and the electronic relaxation mechanism of the low-lying electronic states of the indenyl radical.

Author Correction: A Low-Cost Non-explosive Synthesis of Graphene Oxide for Scalable Applications.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has not been fixed in the paper.

A Low-Cost Non-explosive Synthesis of Graphene Oxide for Scalable Applications.

A low cost, non-explosive process for the synthesis of graphene oxide (GO) is demonstrated. Using suitable choice of reaction parameters including temperature and time, this recipe does not require expensive membranes for filtration of carbonaceous and metallic residues. A pre-cooling protocol is introduced to control the explosive nature of the highly exothermic reactions during the oxidation process. This alleviates the requirement for expensive membranes and completely eliminates the explosive nature of intermediate reaction steps when compared to existing methods. High quality of the synthesized GO is corroborated using a host of characterization techniques including X-ray diffraction, optical spectroscopy, X-ray photoemission spectroscopy and current-voltage characteristics. Simple reduction protocol using ultra-violet light is demonstrated for potential application in the area of photovoltaics. Using different reduction protocols together with the proposed inexpensive method, reduced GO samples with tunable conductance over a wide range of values is demonstrated. Density functional theory is employed to understand the structure of GO. We anticipate that this scalable approach will catalyze large scale applications of GO.

Time-dependent quantum wave packet dynamics of S + OH reaction on its electronic ground state.

Initial state-selected dynamics of the S((3)P) + OH (X(2)Π) → SO (X(3)Σ(-)) + H ((2)S) reaction on its electronic ground potential energy surface (X̃(2)A") is investigated here by a time-dependent wave packet propagation (TDWP) approach. Total reaction probabilities for the three-body rotational angular momentum up to J = 138 are calculated to obtain converged integral reaction cross sections and state-specific rate constants employing the centrifugal sudden (CS) approximation. The convergence of the latter quantities is checked by varying all parameters used in the numerical calculations. The cross section and rate constant results are compared with those available in the literature, calculated with the aid of the quasi-classical trajectory method on the same potential energy surface. Reaction probabilities obtained with the TDWP approach exhibit dense oscillatory structures, implying formation of a metastable quasi-bound complex during the collision process. The effect of rotational and vibrational excitations of reagent OH on the dynamical attributes is also examined. While the rotational excitation of reagent OH decreases the reactivity, its vibrational excitation enhances the same.

Time-dependent quantum wave packet dynamics of the C + OH reaction on the excited electronic state.

Quantum state-selected dynamics of C((3)P) + OH (X(2)Π) → CO(a(3)Π) + H ((2)S) reaction on its first excited electronic potential energy surface (1(2)A(")) is examined here using a time-dependent wave packet propagation approach. All partial wave contributions for the total angular momentum, J = 0-95, are included to obtain the converged cross sections and initial state-selected rate constants in the temperature range of 10-500 K. The reaction probability, as a function of collision energy, exhibits dense oscillatory structures owing to the formation of resonances during collision. These resonance structures also persist in reaction cross sections. The effect of reagent rotational and vibrational excitation on the dynamical attributes is examined and discussed. Reagent rotational excitation decreases the reactivity whereas, vibrational excitation of the reagent has minor effects on the reactivity. The results presented here are in good accord with those obtained using the time-independent quantum mechanical and quasi-classical trajectory methods.

Nuclear motion on the orbitally degenerate electronic ground state of fully deuterated triatomic hydrogen.

Nuclear motion in the vicinity of conical intersections of the degenerate electronic ground state of fully deuterated triatomic hydrogen, D(3), is investigated with the aid of a time-dependent wavepacket approach in hyperspherical coordinates. Vibronic energy level spectra and the eigenfunctions are examined by including, for example, (1) geometric phase (GP) correction, (2) diagonal Born-Huang (BH) correction, and (3) both GP and BH corrections to the Born-Oppenheimer adiabatic Hamiltonian and finally by considering the nonadiabatic coupling between the two electronic surfaces explicitly. It emerges from this study that inclusion of both the GP and BH corrections is insufficient to explain the spectral features observed in the experiment. The latter are recovered by considering the complete two-states coupled Hamiltonian only. This study shows that both the GP and BH corrections constitute a minor part of the surface coupling effects, in particular, on the dynamics of the upper adiabatic sheet. Most importantly, we add that the experimental signature of the GP effect appears only in the observed shift of the eigenlevels of the electronic state when compared to those obtained from a completely Born-Oppenheimer Hamiltonian. The detail fine structure of the observed band of the electronic state is shaped by the off-diagonal derivative coupling elements of the nonadiabatic coupling operator.