Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

Spin-polarized STM spectra of Dirac electrons on the surface of a topological insulator

We provide a theory for the tunneling conductance G(V) of Dirac electrons on the surface of a topological insulator as measured by a spin-polarized scanning tunneling microscope tip for low-bias voltages V. We show that if the in-plane rotational symmetry on the surface of the topological insulator is broken by an external field that does not couple to spin directly (such as an in-plane electric field), G(V) exhibits an unconventional dependence on the direction of the magnetization of the tip, i.e., it acquires a dependence on the azimuthal angle of the magnetization of the tip. We also show that G(V) can be used to measure the magnitude of the local out-of-plane spin orientation of the Dirac electrons on the surface. We explain the role of the Dirac electrons in this unconventional behavior and suggest experiments to test our theory.

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

The reaction of [Cp*TaCl(4)], 1 (Cp* = eta(5)-C(5)Me(5)), with [LiBH(4)center dot THF] at -78 degrees C, followed by thermolysis in the presence of excess [BH(3)center dot THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B(4)H(10)O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe(2)(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B(2)H(4)O{H(2)Fe(2)(CO)(6)BH} ] 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta(2)Fe(2)] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B(4)H(4)Se(2)], 4 was treated with an excess of [Fe(2)(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe(6)(CO)(13)B(2)(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo(2)Se(2)Fe(2)B(2)] and a tricapped trigonal prism [Fe(6)B(3)] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, (1)H, (11)B, (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated (11)B NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.

Nature of Electronic States in Atomically Thin MoS(2) Field-Effect Transistors

We present low-temperature electrical transport experiments in five field-effect transistor devices consisting of monolayer, bilayer, and trilayer MoS(2) films, mechanically exfoliated onto Si/SiO(2) substrate. Our experiments reveal that the electronic states In all films are localized well up to room temperature over the experimentally accessible range of gate voltage. This manifests in two-dimensional (2D) variable range hopping (VRH) at high temperatures, while below similar to 30 K, the conductivity displays oscillatory structures In gate voltage arising from resonant tunneling at the localized sites. From the correlation energy (T(0)) of VRH and gate voltage dependence of conductivity, we suggest that Coulomb potential from trapped charges In the substrate is the dominant source of disorder in MoS(2) field-effect devices, which leads to carrier localization, as well.

Total Factor Productivity in Indian Electronic Sector after Liberalisation: Sources and Outcomes

This paper analyses the efficiency and productivity growth of the Electronic Sector of India in the liberalization era since 1991. The study gives an insight into the process of the growth of one of the most upcoming sector of this decade. This sector has experienced a vast structural change along with the changing economic structures in India after liberalisation. With the opening up of this sector to foreign market and incoming of multinational companies, the environment has become highly competitive. The law that operates is that of Darwin’s ‘Survival of the fittest’. Existing industries experience a continuous threat of exit due to entrance of new potential entrants. Thus, it becomes inevitable for the existing industries in this sector to improve productivity growth for their survival. It is thus important to analyze how the industries in this sector have performed over the years and what are the factors that have contributed to the overall output growth.

Mixed ionic and electronic conduction in zirconia and its applications in metallurgy

Mixed ionic and electronic conduction in Zr02-based solid electrolytes was studied.The effect of impurities and second-phase particles on the mixed conduction parameter, P,, was measured for different types of ZrOZ electrolytes. The performance of solid-state sensors incorporating ZrOZ electrolytes is sometimes limited by electronic conduction in ZrOZ, especially at temperatures >I800 K. Methods for eliminating or minimizing errors in measured emf due to electronically driven transport of oxygen anions are discussed. Examples include probes for monitoring oxygen content in liquid steel as well as the newly developed sulfur sensor based on a ZrOz(Ca0) + CaS electrolyte. The use of mixed conducting ZrOZ as a semipermeable membrane or chemically selective sieve for oxygen at high temperatures is discussed. Oxygen transport from liquid iron to CO + C& gas mixtures through a ZrOZ membrane driven by a chemical potential gradient, in the absence of electrical leads or imposed potentials, was experimentally observed.

Synthesis, characterization and spectroscopy of composites of graphene with CdSe and CdS nanoparticles

Nanocomposites of few-layer graphene with nanoparticles of CdSe and CdS have been synthesized by two different methods, one involving ultrasonication of a mixture of graphene and the chalcogenide nanoparticles, and another involving assembly at the organic-aqueous interface. The nanocomposites have been examined by electron microscopy, electronic absorption and photoluminescence spectroscopies as well as Raman spectroscopy. Electron microscopy reveals that the nanoparticles are dispersed on the graphene surface. Raman spectra show the presence of definitive electronic interaction between the nanoparticles and graphene depending on the capping agent. Photoluminescence spectra are markedly influenced by the interaction of the nanoparticles with the graphene surface, depending on the capping agent.

Development of novel multiple quantummethodologies for the analyses of complex protonNMR spectra of scalar coupled spins

One of the significant advancements in Nuclear Magnetic Resonance spectroscopy (NMR) in combating the problem of spectral complexity for deriving the structure and conformational information is the incorporation of additional dimension and to spread the information content in a two dimensional space. This approach together with the manipulation of the dynamics of nuclear spins permitted the designing of appropriate pulse sequences leading to the evolution of diverse multidimensional NMR experiments. The desired spectral information can now be extracted in a simplified and an orchestrated manner. The indirect detection of multiple quantum (MQ) NMR frequencies is a step in this direction. The MQ technique has been extensively used in the study of molecules aligned in liquid crystalline media to reduce spectral complexity and to determine molecular geometries. Unlike in dipolar coupled systems, the size of the network of scalar coupled spins is not big in isotropic solutions and the MQ 1H detection is not routinely employed,although there are specific examples of spin topology filtering. In this brief review, we discuss our recent studies on the development and application of multiple quantum correlation and resolved techniques for the analyses of proton NMR spectra of scalar coupled spins.

The interaction of halogen molecules with SWNTs and graphene

The interaction of halogen molecules of varying electron affinity, such as iodine monochloride (ICl), bromine (Br(2)), iodine monobromide (IBr) and iodine (I(2)) with single-walled carbon nanotubes (SWNTs) and graphene has been investigated in detail. Halogen doping of the two nanocarbons has been examined using Raman spectroscopy in conjunction with electronic absorption spectroscopy and extensive theoretical calculations. The halogen molecules, being electron withdrawing in nature, induce distinct changes in the electronic states of both the SWNTs and graphene, which manifests with a change in the spectroscopic signatures. Stiffening of the Raman G-bands of the nanocarbons upon treatment with the different halogen molecules and the emergence of new bands in the electronic absorption spectra, both point to the fact that the halogen molecules are involved in molecular charge-transfer with the nanocarbons. The experimental findings have been explained through density functional theory (DFT) calculations, which suggest that the extent of charge-transfer depends on the electron affinities of the different halogens, which determines the overall spectroscopic properties. The magnitude of the molecular charge-transfer between the halogens and the nanocarbons generally varies in the order ICl > Br(2) > IBr > I(2), which is consistent with the expected order of electron affinities.

Full spin and spatial symmetry adapted technique for correlated electronic hamiltonians: Application to an icosahedral cluster

One of the long standing problems in quantum chemistry had been the inability to exploit full spatial and spin symmetry of an electronic Hamiltonian belonging to a non-Abelian point group. Here, we present a general technique which can utilize all the symmetries of an electronic (magnetic) Hamiltonian to obtain its full eigenvalue spectrum. This is a hybrid method based on Valence Bond basis and the basis of constant z-component of the total spin. This technique is applicable to systems with any point group symmetry and is easy to implement on a computer. We illustrate the power of the method by applying it to a model icosahedral half-filled electronic system. This model spans a huge Hilbert space (dimension 1,778,966) and in the largest non-Abelian point group. The C60 molecule has this symmetry and hence our calculation throw light on the higher energy excited states of the bucky ball. This method can also be utilized to study finite temperature properties of strongly correlated systems within an exact diagonalization approach. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

Synthesis, X-ray crystal structure, DNA binding, antioxidant and cytotoxicity studies of Ni(II) and Pd(II) thiosemicarbazone complexes

New complexes, [Ni(HL)(PPh3)]Cl (1), [Pd(L)(PPh3)](2), and [Pd(L)(AsPh3)](3), were synthesized from the reactions of 4-chloro-5-methyl-salicylaldehyde thiosemicarbazone [H2L] with [NiCl2(PPh3)(2)], [PdCl2(PPh3)(2)] and [PdCl2(AsPh3)(2)]. They were characterized by IR, electronic, H-1-NMR spectral data. Further, the structures of the complexes have been determined by single crystal X-ray diffraction. While the thiosemicarbazone coordinated as binegative tridentate (ONS) in complexes 2 and 3, it is coordinated as mono negative tridentate (ONS) in 1. The interactions of the new complexes with calf thymus DNA was examined by absorption and emission spectra, and viscosity measurements. Moreover, the antioxidant properties of the new complexes have also been tested against DPPH radical in which complex 1 exhibited better activity than that of the other two complexes 2 and 3. The in vitro cytotoxicity of complexes 1-3 against A549 and HepG2 cell lines was assayed, and the new complexes exhibited higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations.

Electronic structure of early transition metal oxides, Ca1−xSrxVO3 and La1−xCaxVO3: What can we learn from photoelectron spectroscopy

Photoemission spectroscopy offers the unique possibility of mapping out the electronic structure of the occupied electron states. However, the extreme surface sensitivity of this technique ensures that only the surface and the near-surface regions of any sample are probed. An important question arises in this context—Is the electronic structure of the surface region the same as that of the bulk? We address this issue using two different series of vanadium oxides, Ca1−xSrxVO3 and La1−xCaxVO3. Our results clearly establish that the electronic structure of the surface region is drastically different from that of the bulk in both these cases. We provide a method to separate the two contributions: one arising from the near-surface region and the other representative of the bulk. This separation allows us to deduce some very unusual behaviors of the electronic structures in these systems.

Simple theoretical analysis of the photoemission from quantum confined effective mass superlattices of optoelectronic materials

The photoemission from quantum wires and dots of effective mass superlattices of optoelectronic materials was investigated on the basis of newly formulated electron energy spectra, in the presence of external light waves, which controls the transport properties of ultra-small electronic devices under intense radiation. The effect of magnetic quantization on the photoemission from the aforementioned superlattices, together with quantum well superlattices under magnetic quantization, has also been investigated in this regard. It appears, taking HgTe/Hg1-xCdxTe and InxGa1-xAs/InP effective mass superlattices, that the photoemission from these quantized structures is enhanced with increasing photon energy in quantized steps and shows oscillatory dependences with the increasing carrier concentration. In addition, the photoemission decreases with increasing light intensity and wavelength as well as with increasing thickness exhibiting oscillatory spikes. The strong dependence of the photoemission on the light intensity reflects the direct signature of light waves on the carrier energy spectra. The content of this paper finds six different applications in the fields of low dimensional systems in general.

Pressure induced phase transition in metallic LaB6: A Raman study

We report high pressure Raman studies on single crystals of metallic LaB6 upto a pressure of 16.$ GPa. Raman spectra shows three lines at 680 cm(-1) (T-2g), 1120 cm(-1) (E-g) and 1258 cm(-1) (A(1g)), associated with the internal modes of B-6 molecule. The T-2g mode shows an asymmetric Fano line shape, arising from the interference between the phonon line and the electronic continuum. The line is fitted with I(omega) = I-0(q + epsilon(2))/(I + epsilon(2)) where epsilon = (omega - omega(0))/Gamma, omega(0) is the phonon frequency renormalised due to electron-phonon self energy corrections, Tis the width parameter proportional to the square of the matrix element of the electron-phonon interaction potential. The parameter a signifies the strength of interference. Most interestingly our pressure data for the T-2g mode shows a significant change in the slope of the mode frequency with pressure d omega(0)/dP and Gamma at 9.5 GPa. This clearly indicates that LaB6 undergoes a subtle phase transition at 9.5 GPa within the metallic phase.