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.

Model for Predicting the Mean Drop Size in Effervescent Sprays

This paper is focused on the development of a model for predicting the mean drop size in effervescent sprays. A combinatorial approach is followed in this modeling scheme, which is based on energy and entropy principles. The model is implemented in cascade in order to take primary breakup (due to exploding gas bubbles) and secondary breakup (due to shearing action of surrounding medium) into account. The approach in this methodology is to obtain the most probable drop size distribution by maximizing the entropy while satisfying the constraints of mass and energy balance. The comparison of the model predictions with the past experimental data is presented for validation. A careful experimental study is conducted over a wide range of gas-to-liquid ratios, which shows a good agreement with the model predictions: It is observed that the model gives accurate results in bubbly and annular flow regimes. However, discrepancies are observed in the transitional slug flow regime of the atomizer.

Analysis of Lined Ducts With Mean Flow, With Application to Dissipative Mufflers

Mufflers with at least one acoustically absorptive duct are generally called dissipative mufflers. Generally, for want of systems approach, these mufflers are characterized by transmission loss of the lined duct with overriding corrections for the terminations, mean flow, etc. In this article, it is proposed that dissipative duct should be integrated with other muffler elements, source impedance and radiation impedance, by means of transfer matrix approach. Towards this end, the transfer matrix for rectangular duct with mean flow has been derived here, for the least attenuated mode. Mean flow introduces a coupling between transverse wave numbers and axial wave number, the evaluation of which therefore calls for simultaneous solution of two or three transcendental equations. This is done by means of a Newton-Raphson iteration scheme, which is illustrated here for square ducts lined with porous ceramic tiles.

Transfer matrix modeling of hyperbolic and parabolic ducts with incompressible mean flow

A general differential equation for the propagation of sound in a variable area duct or nozzle carrying incompressible mean flow (of low Mach number) is derived and solved for hyperbolic and parabolic shapes. Expressions for the state variables of acoustic pressure and acoustic mass velocity of the shapes are derived. Self‐consistent expressions for the four‐pole parameters are developed. The conical, exponential, catenoidal, sine, and cosine ducts are shown to be special cases of hyperbolic ducts. Finally, it is shown that if the mean flow in computing the transmission loss of the mufflers involving hyperbolic and parabolic shapes was not neglected, little practical benefit would be derived.

Tip Motion Control and Scanning of a Reorientable Micromanipulator With Axially Located Tip

Two-axis micromanipulators, whose tip orientation and position can be controlled in real time in the scanning plane, enable versatile probing systems for 2.5-D nanometrology. The key to achieve high-precision probing systems is to accurately control the interaction point of the manipulator tip when its orientation is changed. This paper presents the development of a probing system wherein the deviation in the end point due to large orientation changes is controlled to within 10 nm. To achieve this, a novel micromanipulator design is first proposed, wherein the end point of the tip is located on the axis of rotation. Next, the residual tip motion caused by fabrication error and actuation crosstalk is modeled and a systematic method to compensate it is presented. The manipulator is fabricated and the performance of the developed scheme to control tip position during orientation change is experimentally validated. Subsequently, the two-axis probing system is demonstrated to scan the full top surface of a micropipette down to a diameter of 300 nm.

Modeling of growth and motion of equiaxed dendrites in a convecting melt

A numerical micro-scale model is developed to study the behavior of dendrite growth in presence of melt convection. In this method, an explicit, coupled enthalpy model is used to simulate the growth of an equiaxed dendrite, while a Volume of Fluid (VOF) method is used to track the movement of the dendrite in the convecting melt in a two-dimensional Eulerian framework. Numerical results demonstrate the effectiveness of the enthalpy model in simulating the dendritic growth involving complex shape, and the accuracy of VOF method in conserving mass and preserving the complex dendritic shape during motion. Simulations are performed in presence of uniform melt flow for both fixed and moving dendrites, and the difference in dendrite morphology is shown.

Time-frequency analysis of human motion during rhythmic exercises

Biomechanical signals due to human movements during exercise are represented in time-frequency domain using Wigner Distribution Function (WDF). Analysis based on WDF reveals instantaneous spectral and power changes during a rhythmic exercise. Investigations were carried out on 11 healthy subjects who performed 5 cycles of sun salutation, with a body-mounted Inertial Measurement Unit (IMU) as a motion sensor. Variance of Instantaneous Frequency (I.F) and Instantaneous Power (I.P) for performance analysis of the subject is estimated using one-way ANOVA model. Results reveal that joint Time-Frequency analysis of biomechanical signals during motion facilitates a better understanding of grace and consistency during rhythmic exercise.

Electron paramagnetic resonance study of porous silicon

Electron paramagnetic resonance studies under ambient conditions of boron‐doped porous silicon show anisotropic Zeeman (g) and hyperfine (A) tensors, signaling localization of the charge carriers due to quantum confinement.

Experimental implementation of quantumUlam’s problem in a nuclear magnetic resonance quantum information processor

The Ulam’s problem is a two person game in which one of the player tries to search, in minimum queries, a number thought by the other player. Classically the problem scales polynomially with the size of the number. The quantum version of the Ulam’s problem has a query complexity that is independent of the dimension of the search space. The experimental implementation of the quantum Ulam’s problem in a Nuclear Magnetic Resonance Information Processor with 3 quantum bits is reported here.

An analogue of the Wiener Tauberian Theorem for the Heisenberg Motion group

We show that the Wiener Tauberian property holds for the Heisenberg Motion group TnB

Frequency response analysis of layered ground in Ahmedabad during Bhuj earthquake

This paper presents the results of seismic response analysis of layered ground in Ahmedabad City during the earthquake in Bhuj on 26(th) January 2001. An attempt has been made to understand the reasons for the failure of multistoreyed buildings founded on soft alluvial deposits in Ahmedabad. Standard Penetration test at a site very close to the Sabarmati river belt was carried out for geotechnical investigations. The program SHAKE91, widely used in the field of earthquake engineering for computing the seismic response of horizontally layered soil deposits, was used to analyse the soil profile at the selected site considering the ground as one dimensional layered elastic system. The ground accelerations recorded at the ground floor of the Regional Passport Staff Quarters building, which is very close to the investigated site, was used as input motion. Also, Finite Element Analysis was carried out for different configurations of multistorey building frames for evaluating their natural frequencies and is compared with the predominant frequency of the layered soil system. The results reveal that the varying degree of damage to multistorey buildings in the close proximity of Sabarmati river area was essentially due to the large amplification of the ground and the near resonance condition.