Selection rules and symmetry relations for four-wave mixing measurements of uniaxial assemblies

Uniaxial systems represent the next lowest symmetry below isotropic and are ubiquitous. The objective of the present work is to present a systematic foundation for interpreting polarization-dependent four-wave mixing measurements of oriented and aligned assemblies. Orientational averages connecting the molecular frame to the macroscopic frame in uniaxial assemblies were derived for several common molecular symmetry groups for coherent anti-Stokes Raman spectroscopy (CARS) measurements, coherent anti-Stokes two-photon spectroscopy (CATS) probing electronic transitions, resonant two-photon absorption (2PA), and traditional Raman measurements. First, the complete set of orientational averages connecting the molecular and macroscopic frames was compiled for the most general case of C1 molecular symmetry. Then, the orientational averages of a select few commonly occurring molecular symmetry groups (Cs, C2, C2v, and C3v) were explored in greater detail to illustrate the approach and to facilitate the interpretation of routine experimental measurements. One outcome of this analysis is the prediction of efficient electric dipole-allowed chiral-specific four-wave mixing in uniaxially oriented media.     

Shape resonances in slow electron scattering by aromatic molecules. I. Anthraquinone derivatives

A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd.     

A finite element formulation for global linear stability analysis of a nominally two‐dimensional base flow

A stabilized finite element method, to carry out the linear stability analysis of a two‐dimensional base flow to three‐dimensional perturbations that are periodic along span, is presented. The resulting equations for the time evolution of the disturbance requires a solution to the generalized eigenvalue problem. The analysis is global in nature and is also applicable to non‐parallel flows. Equal‐order‐interpolation functions for velocity and pressure are utilized. Stabilization terms are added to the Galerkin formulation to admit the use of equal‐order‐interpolation functions and to eliminate node‐to‐node oscillations that might arise in advection‐dominated flows. The proposed formulation is tested on two flow problems. First, the mode transitions in the circular Couette flow are investigated. Two scenarios are considered. In the first one, the outer cylinder is at rest, while the inner one spins. Two linearly unstable modes are identified. The primary mode is real and represents the axisymmetric Taylor vortices. The second mode is complex and consists of spiral vortices. For the counter‐rotating cylinders, the primary transition is via the appearance of spiral vortices. Excellent agreement with results from earlier studies is observed. The formulation is also utilized to investigate the parallel and oblique modes of vortex shedding past a cylinder for the Re = 100 flow. It is found that the flow is associated with a large number of unstable oblique shedding modes. The parallel mode of vortex shedding is a special case of this family of modes and is associated with the largest growth rate. Copyright © 2014 John Wiley & Sons, Ltd.     

NLOPredict: visualization and data analysis software for nonlinear optics

A data analysis and visualization program was developed to assist in the interpretation of second-order nonlinear optical (NLO) processes, including vibrational sum-frequency generation and electronically resonant second harmonic generation. A novel diagrammatic approach allows concise visual representations of the resonant NLO molecular response. By mapping the predicted NLO response as a function of molecular orientation, molecular modeling results can be combined with experimental measurements for orientational analysis. A method is developed and implemented to predict the nonlinear optical properties of the amide backbones in complete proteins with known structures. NLOPredict is available for most computer operating systems from http://sda.iu.edu/nlopredict/.     

Oscillator models for multiphoton optical bistability and phase conjugacy

Nonlinear oscillator models are constructed to treat the bistability in situations involving elementary excitations in solids. Such models are shown to be useful not only in describing single photon but also multiphoton bistability. The resulting bistability both with and without cavity is considered. The two-photon excitonic bistability in CuCl is in detail. The effect of local field corrections can also be incorporated, in a simple manner, in such models.