Group-theoretical investigation of the tunneling splitting patterns of enolic acetylacetone

Extensive experimental and theoretical studies for enolic acetylacetone have been presented in the literature, but studies of the tunneling splitting patterns are still lacking. In this work we adopt the C_s symmetry equilibrium structure and apply a group-theoretical formalism to study the tunneling splitting pattern of the ground vibrational level of enolic acetylacetone. Enolic acetylacetone has three large-amplitude motions, one intramolecular hydrogen transfer and two methyl torsions. Therefore, the C_s structure of enolic acetylacetone has 18 (3 × 3 × 2) equivalent equilibrium molecular frameworks, nine (3 × 3) of them are from the two methyl torsions, and two are from the intramolecular hydrogen transfer. Tunneling motions among the 18 equivalent molecular frameworks split the ground vibrational level into eight sublevels: A₁, A₄, E₁, E₂, E₃, E₄, G(1) and G(2). In enolic acetylacetone the intramolecular hydrogen transfer induces a rearrangement of the CC, CO single and double bonds, and then triggers two additional 60° internal rotations, one in each of the two methyl groups attached to the hydrogen-bonded malonaldehyde ring. This interaction further complicates the tunneling splitting patterns and increases the difficulty of spectral analysis. In this work the influence of the intramolecular hydrogen transfer on the energy order of the eight sublevels is determined by a group-theoretical formalism.     

Four complementary theoretical approaches for the analysis of NMR paramagnetic relaxation

Four theoretical and computational approaches used at the University of Michigan to analyze NMR paramagnetic relaxation enhancement (NMR-PRE) are described. The primary objective of the theory is to describe the relationship of the NMR-PRE phenomenon to the electron spin hamiltonian and the spin energy level structure when zero field splitting interactions are significant. Four formulations of theory are discussed: (1) spin dynamics simulation; (2) the laboratory frame "constant H(S)" formulation; (3) the Molecular Frame "constant H(S)" formulation; and (4) the zfs-limit "constant H(S)" formulation. No single theoretical approach describes all important aspects of the relaxation mechanism in a fully satisfactory way. We use the four formulations in a complementary manner to provide as complete a picture of the relaxation mechanism as possible. We also discuss the integration of NMR-PRE theory and recently developed theory of electron spin relaxation which accounts for effects of the permanent zfs hamiltonian.     

TheB 2Σ-X 2Σ system of the CaF molecule

The spectrum of theB ²Σ-X ²Σ system of the CaF molecule has been photographed in the second order of a 10.6 m concave grating spectrograph with 0.33 Å/mm dispersion. The rotational structure of the (0, 0) and (1, 0) bands has been analysed and the precise molecular constants have been obtained. Using the constants so determined the band origins of a large number of bands with 0 <v′,v″ < 10 have been calculated and used to obtain the accurate vibrational constants forB andX states and these are presented.     

On the efficiency of selection criteria in spline regression

This paper concerns the cubic smoothing spline approach to nonparametric regression. After first deriving sharp asymptotic formulas for the eigenvalues of the smoothing matrix, the paper uses these formulas to investigate the efficiency of different selection criteria for choosing the smoothing parameter. Special attention is paid to the generalized maximum likelihood (GML), C _p and extended exponential (EE) criteria and their marginal Bayesian interpretation. It is shown that (a) when the Bayesian model that motivates GML is true, using C _p to estimate the smoothing parameter would result in a loss of efficiency with a factor of 10/3, proving and strengthening a conjecture proposed in Stein (1990); (b) when the data indeed come from the C _p density, using GML would result in a loss of efficiency of ; (c) the loss of efficiency of the EE criterion is at most 1.543 when the data are sampled from its consistent density family. The paper not only studies equally spaced observations (the setting of Stein, 1990), but also investigates general sampling scheme of the design points, and shows that the efficiency results remain the same in both cases.This work is supported in part by NSF grant DMS-0204674 and Harvard University Clark-Cooke Fund. Mathematics Subject Classification (2000):Primary: 62G08; Secondary: 62G20     

Sequential estimation of a parameter of an exponential distribution

We consider the problem of minimum risk point estimation for the parameter =a+b of the exponential distribution with unknown location parameter and scale parameter when the loss function is squared error plus linear cost. In this paper, we propose a sequential estimator of and show that the associated risk is asymptotically one cost less than that given by Ghosh and Mukhopadhyay (1989,South African Statist. J.,23, 251–268).     

Bayesian sequential reliability for Weibull and related distributions

Assume that the probability density function for the lifetime of a newly designed product has the form: [H(t)/Q()] exp{–H(t)/Q()}. The Exponential(), Rayleigh, WeibullW(, ) and Pareto pdf's are special cases.Q() will be assumed to have an inverse Gamma prior. Assume thatm independent products are to be tested with replacement. A Bayesian Sequential Reliability Demonstration Testing plan is used to eigher accept the product and start formal production, or reject the product for reengineering. The test criterion is the intersection of two goals, a minimal goal to begin production and a mature product goal. The exact values of various risks and the distribution of total number of failures are evaluated. Based on a result about a Poisson process, the expected stopping time for the exponential failure time is also found. Included in these risks and expected stopping times are frequentist versions, thereof, so that the results also provide frequentist answers for a class of interesting stopping rules.This research was supported by NSF grants DMS-8703620 and DMS-8923071, and forms part of the Ph.D. Thesis of the first author, the development of which was supported in part by a David Ross grant at Purdue University. The authors thank the editors and a referee for insightful comments and suggestions.     

Mossbauer study of ferrite systems Co x Mn1−x Fe2O4 and Ni x Mn1−x Fe2O4

Mössbauer spectra of Co _x Mn_1?x Fe₂O₄ and Ni _x Mn_1?x Fe₂O₄ ferrites withx values ranging from 0·1 to 0·8 in steps of 0·1 have been recorded at room temperature. All spectra exhibit well-defined Zeeman hyperfine patterns. It has been observed that hyperfine field at Fe³⁺ nucleus increases more rapidly by nickel substitution than by cobalt substitution. This has been explained in terms of exchange interactions and cation distribution in the spinels. Hyperfine fields, isomer shifts and quadrupole splittings have been determined.     

Design and optimal tuning of nonlinear PI compensators

In this paper, linear time-invariant single-input single-output (SISO) systems that are stabilizable by linear proportional and integral (PI) compensators are considered. For such systems, a five-parameter nonlinear PI compensator is proposed. The parameters of the proposed compensator are tuned by solving an optimization problem. The optimization problem always has a solution.Additionally, a general nonlinear PI compensator is proposed and is approximated by easy-to-compute compensators, for instance, a six-parameter nonlinear PI compensator. The parameters of the approximate compensators are tuned to satisfy an optimality condition. The superiority of the proposed nonlinear PI compensators over linear PI compensators is discussed and is demonstrated for two feedback systems.     

Effects of initial frequency chirp on the linear propagation characteristics of the exponential optical pulse

In this paper, the linear propagation characteristics of the exponential optical pulse with initial linear and nonlinear frequency chirp are numerically studied in a single mode fibre for \be₂<0. It can be found that the temporal full width at half maximum and time-bandwidth product of exponential pulse monotonically increase with the increase of propagation distance and decrease with the increase of linear chirp C for C<0.5, go through an initial decreasing stage near \zeta=1, then increase with the increase of propagation distance and linear chirp C for C\geq0.5. The broadening of pulses with negative chirp is faster than that with positive chirp. The exponential pulse with linear chirp gradually evolves into a near-Gaussian pulse. The effect of nonlinear chirp on waveform of the pulse is much greater than that of linear chirp. The temporal waveform breaking of exponential pulse with nonlinear chirp is first observed in linear propagation. Furthermore, the expressions of the spectral width and time-bandwidth product of the exponential optical pulse with the frequency chirp are given by use of the numerical analysis method.