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11.
Thorwirth S McCarthy MC Gottlieb CA Thaddeus P Gupta H Stanton JF 《The Journal of chemical physics》2005,123(5):054326
The sulfur molecules thiozone S3 and tetrasulfur S4 have been observed in a supersonic molecular beam in the centimeter-wave band by Fourier transform microwave spectroscopy, and in the millimeter- and submillimeter-wave bands in a low-pressure glow discharge. For S3 over 150 rotational transitions between 10 and 458 GHz were measured, and for S4 a comparable number between 6 and 271 GHz. The spectrum of S3 is reproduced to within the measurement uncertainties by an asymmetric top Hamiltonian with three rotational and 12 centrifugal distortion constants; ten distortion constants, but an additional term to account for very small level shifts caused by interchange tunneling, are required to reproduce to comparable accuracy the spectrum of S4. Empirical equilibrium (r(e)(emp)) structures of S3 and S4 were derived from experimental rotational constants of the normal and sulfur-34 species and vibrational corrections from coupled-cluster theory calculations. Quantum chemical calculations show that interchange tunneling occurs because S4 automerizes through a transition state with D2h symmetry which lies about 500 cm(-1) above the two equivalent C2upsilon minima on the potential energy surface. 相似文献
12.
Noel V. Stanton Tracy Fritsch Ciaran Geraghty Mary Frances Verostek Bruce Weiner Patrick J. Parsons 《Accreditation and quality assurance》2006,11(11):590-592
Following implementation of the CLIA ‘88 laboratory regulations, the primary role of proficiency testing (external quality assessment, PT) in the U.S. has been widely viewed as one of assuring regulatory compliance. PT can also be an effective tool for detecting widespread analytical problems, subject to limitations based on the method of PT assigned value determination. A recent case study describes the role of two PT programs in detecting and resolving a calibration bias in the LeadCare blood lead analyzer, and illustrates the limitations of peer-group target determination in fulfilling that PT role. 相似文献
13.
Katharine G. Lunny Yanice Benitez Yishai Albeck Prof. Daniel Strasser Prof. John F. Stanton Prof. Robert E. Continetti 《Angewandte Chemie (International ed. in English)》2018,57(19):5394-5397
In an effort to characterize the electronic states of ethylenedione, OCCO, photoelectron‐photofragment coincidence (PPC) spectroscopy was applied to measure anions at m/z 56 and 57 using a pulsed discharge of glyoxal vapor and N2O. PPC measurements at a photon energy of 3.20 eV yield photoelectron spectra in coincidence with either neutral photofragments or stable neutral products. The measurements showed that primarily stable neutral products were formed, with photoelectron spectra consistent with the oxyallyl diradical, C3H4O, and acetone enolate radical, C3H5O. The spectra were also found to have features nearly identical to those reported for OCCO and HOCCO by Sanov and co‐workers. The stability of the neutral products, as well as an examination of spectra reported for the oxyallyl anion and acetone enolate show that the previous assignments of OCCO and HOCCO are in error, and are instead attributed here to the oxyallyl diradical, C3H4O, and the acetone enolate radical, C3H5O. 相似文献
14.
Self-assembling Dimeric and Trimeric Aggregates Based on Solvophobic and Charge-pairing Interactions
Self-assembly processes based on shape complementarity and noncovalent binding interactions are widely recognized as a fundamental principle in nature. Besides charge pairing and hydrogen bonding, hydrophobic interactions play a crucial role in water. Here we report the self-assembly of structurally simple monomers to yield defined dimeric and trimeric aggregates in highly polar media, based on ionic and solvophobic interactions. NMR, mass spectrometry and curve fitting were used to characterize these supramolecular assemblies in water–methanol solutions. 相似文献
15.
16.
Dennis Stanton 《The Ramanujan Journal》2009,19(1):107-113
Two q-analogues of Euler’s theorem on integer partitions with odd or distinct parts are given. A q-lecture hall theorem is given.
Supported by NSF grant DMS-0503660. 相似文献
17.
In this self-contained exposition, results are developed concerning one-factorizations of complete graphs, and incidence matrices are used to turn these factorization results into embedding theorems on Steiner triple systems. The result is a constructive graphical proof that a Steiner triple system exists for any order congruent to 1 or 3 modulo 6. A pairing construction is then introduced to show that one can also obtain triple systems which are cyclically generated. 相似文献
18.
Theq-Krawtchouk polynomials are the spherical functions for three different Chevalley groups over a finite field. Using techniques of Dunkl to decompose the irreducible representations with respect to a maximal parabolic subgroup, we derive three addition theorems. The associated polynomials are related to affine matrix groups.During the preparation of this paper the author was partially supported by NSF grant MCS78-02410. 相似文献
19.
The vertical excitation energy for the lowest valence pi-->pi(*) transition of cyclopentadiene is investigated. Using a combination of high-level theoretical methods and spectroscopic simulations, the vertical separation at the ground state geometry is estimated to be 5.43+/-0.05 eV. This value is intermediate between those calculated with coupled-cluster and multireference perturbation theory methods and is about 0.13 eV higher than the observed maximum in the absorption profile. 相似文献
20.
Recent laboratory measurements of acoustic backscattering by individual benthic shells have isolated the edge-diffracted echo from echoes due to the surface of the main body of the shell. The data indicate that the echo near broadside incidence is generally the strongest for all orientations and is due principally to the surface of the main body. At angles well away from broadside, the echo levels are lower and are due primarily to the diffraction from the edge of the shell. The decrease in echo levels from broadside incidence to well off broadside is shown to be reasonably consistent with the decrease in acoustic backscattering from normal incidence to well off normal incidence by a shell-covered seafloor. The results suggest the importance of the edge of the shell in off-normal-incidence backscattering by a shell-covered seafloor. Furthermore, when considering bistatic diffraction by edges, there are implications that the edge of the shell (lying on the seafloor) can cause significant scattering in many directions, including at subcritical angles. 相似文献