Post-CCSD(T) corrections to bond distances and vibrational frequencies: the power of Λ\Lambda

The importance of post-CCSD(T) corrections as high as CCSDTQ56 for ground-state spectroscopic constants ($D_e$, $\omega_e$, $\omega_ex_e$, and $\alpha_e$) has been surveyed for a sample of two dozen mostly heavy-atom diatomics spanning a broad range of static correlation strength. While CCSD(T) is known to be an unusually felicitous `Pauling point' between accuracy and computational cost, performance leaves something to be desired for molecules with strong static correlation. We find CCSDT(Q)$_\Lambda$ to be the next `sweet spot' up, of comparable or superior quality to the much more expensive CCSDTQ. A similar comparison applies to CCSDTQ(5)$_\Lambda$ vs. CCSDTQ5, while CCSDTQ5(6)$_\Lambda$ is essentially indistinguishable from CCSDTQ56. A composite of CCSD(T)-X2C/ACV5Z-X2C with [CCSDT(Q)$_\Lambda$ -- CCSD(T)]/cc-pVTZ or even cc-pVDZ basis sets appears highly effective for computational vibrational spectroscopy. Unlike CCSDT(Q) which breaks down for the ozone vibrational frequencies, CCSDT(Q)$_\Lambda$ handles them gracefully.Comment: Mol. Phys., in press [Timothy J. Lee memorial issue

Sound scattering by several zooplankton groups. I. Experimental determination of dominant scattering mechanisms

Author Posting. © Acoustical Society of America, 1998. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 103 (1998): 225-235, doi:10.1121/1.421469.The acoustic scattering properties of live individual zooplankton from several gross anatomical groups have been investigated. The groups involve (1) euphausiids (Meganyctiphanes norvegica) whose bodies behave acoustically as a fluid material, (2) gastropods (Limacina retroversa) whose bodies include a hard elastic shell, and (3) siphonophores (Agalma okeni or elegans and Nanomia cara) whose bodies contain a gas inclusion (pneumatophore). The animals were collected from ocean waters off New England (Slope Water, Georges Bank, and the Gulf of Maine). The scattering properties were measured over parts or all of the frequency range 50 kHz to 1 MHz in a laboratory-style pulse-echo setup in a large tank at sea using live fresh specimens. Individual echoes as well as averages and ping-to-ping fluctuations of repeated echoes were studied. The material type of each group is shown to strongly affect both the overall echo level and pattern of the target strength versus frequency plots. In this first article of a two-part series, the dominant scattering mechanisms of the three animal types are determined principally by examining the structure of both the frequency spectra of individual broadband echoes and the compressed pulse (time series) output. Other information is also used involving the effect on overall levels due to (1) animal orientation and (2) tissue in animals having a gas inclusion (siphonophores). The results of this first paper show that (1) the euphausiids behave as weakly scattering fluid bodies and there are major contributions from at least two parts of the body to the echo (the number of contributions depends upon angle of orientation and shape), (2) the gastropods produce echoes from the front interface and possibly from a slow-traveling circumferential (Lamb) wave, and (3) the gas inclusion of the siphonophore dominates the echoes, but the tissue plays a role in the scattering and is especially important when analyzing echoes from individual animals on a ping-by-ping basis. The results of this paper serve as the basis for the development of acoustic scattering models in the companion paper [Stanton et al., J. Acoust. Soc. Am. 103, 236–253 (1998)].This work was supported by the National Science Foundation Grant No. OCE- 9201264, the U.S. Office of Naval Research Grant Nos. N00014-89-J-1729 and N00014-95-1-0287, and the MIT/ WHOI Joint Graduate Education Program

Three-dimensional modeling of acoustic backscattering from fluid-like zooplankton

Author Posting. © Acoustical Society of America, 2002. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 111 (2002): 1197-1210, doi:10.1121/1.1433813.Scattering models that correctly incorporate organism size and shape are a critical component for the remote detection and classification of many marine organisms. In this work, an acoustic scattering model has been developed for fluid-like zooplankton that is based on the distorted wave Born approximation (DWBA) and that makes use of high-resolution three-dimensional measurements of the animal's outer boundary shape. High-resolution computerized tomography (CT) was used to determine the three-dimensional digitizations of animal shape. This study focuses on developing the methodology for incorporating high-resolution CT scans into a scattering model that is generally valid for any body with fluid-like material properties. The model predictions are compared to controlled laboratory measurements of the acoustic backscattering from live individual decapod shrimp. The frequency range used was 50 kHz to 1 MHz and the angular characteristics of the backscattering were investigated with up to a 1° angular resolution. The practical conditions under which it is necessary to make use of high-resolution digitizations of shape are assessed.This work was supported in part by the Woods Hole Oceanographic Institution Education Office

Discovery of SiCSi in IRC+10216: A missing link between gas and dust carriers of SiC bonds

We report the discovery in space of a disilicon species, SiCSi, from observations between 80 and 350 GHz with the IRAM 30m radio telescope. Owing to the close coordination between laboratory experiments and astrophysics, 112 lines have now been detected in the carbon-rich star CWLeo. The derived frequencies yield improved rotational and centrifugal distortion constants up to sixth order. From the line profiles and interferometric maps with the Submillimeter Array, the bulk of the SiCSi emis- sion arises from a region of 6 arcseconds in radius. The derived abundance is comparable to that of SiC2. As expected from chemical equilibrium calculations, SiCSi and SiC2 are the most abundant species harboring a SiC bond in the dust formation zone and certainly both play a key role in the formation of SiC dust grains.Comment: To be published in the Astrophysical Journal Letters; Accepted May 6 201

Effect of orientation on broadband acoustic scattering of Antarctic krill Euphausia superba : implications for inverting zooplankton spectral

Author Posting. © Acoustical Society of America, 1998. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 104 (1998): 2121-2135, doi:10.1121/1.423726.Acoustic scattering experiments involving simultaneous acquisition of broadband echoes and video footage from several Antarctic krill were carried out to determine the effect of animal orientation on echo spectral structure. A novel video analysis technique, applied to extract krill angle of orientation corresponding to each insonification, revealed that echo spectra from krill near broadside incidence relative to the incident acoustic wave exhibited widely spaced, deep nulls, whereas off-broadside echo spectra had a more erratic structure, with several closely spaced nulls of variable depth. The pattern of changes in echo spectra with orientation for the experimentally measured acoustic returns was very similar to theoretically predicted patterns based on a distorted wave Born approximation (DWBA) model. Information contained in the broadband echo spectra of the krill was exploited to invert the acoustic returns for angle of orientation by applying a newly developed Covariance Mean Variance Classification (CMVC) approach, using generic and animal-specific theoretical and empirical model spaces. The animal-specific empirical model space was best able to invert for angle of orientation. The CMVC inversion technique can be implemented using a generic empirical model space to determine angle of orientation based on broadband echoes from individual zooplankton in the field.L.V.MT.’s research was supported by the Ocean Acoustics, Oceanic Biology and URIP programs of the Office of Naval Research Grant Nos. N00014-89-J-1729, N00014-95-1-0287, and N00014-92-J-1527, the Biological Oceanography program of the National Science Foundation Grant No. OCE-9201264, and the WHOI/MIT Joint Program Education Office

Surgical management of life threatening events caused by intermittent aortic insufficiency in a native valve: case report

We describe a case of a patient admitted with apparent life threatening events characterized by hypotension and bradycardia. The patient was ultimately found to have intermittent severe aortic insufficiency. Upon surgical exploration, abnormalities were discovered in the aortic valve, which had a small left coronary cusp with absence of the nodulus of Arantius. Following surgical repair of the valve, aimed at preventing the small cusp from becoming stuck in the open position, the patient has remained episode free for over one year

Peptide Fragments of a β-Defensin Derivative with Potent Bactericidal Activity

β-Defensins are known to be both antimicrobial and able to chemoattract various immune cells. Although the sequences of paralogous genes are not highly conserved, the core defensin structure is retained. Defb14-1C(V) has bactericidal activity similar to that of its parent peptide (murine β-defensin Defb14) despite all but one of the canonical six cysteines being replaced with alanines. The 23-amino-acid N-terminal half of Defb14-1C(V) is a potent antimicrobial while the C-terminal half is not. Here, we use a library of peptide derivatives to demonstrate that the antimicrobial activity can be localized to a particular region. Overlapping fragments of the N-terminal region were tested for their ability to kill Gram-positive and Gram-negative bacteria. We demonstrate that the most N-terminal fragments (amino acids 1 to 10 and 6 to 17) are potent antimicrobials against Gram-negative bacteria whereas fragments based on sequence more C terminal than amino acid 13 have very poor activity against both Gram-positive and -negative types. We further test a series of N-terminal deletion peptides in both their monomeric and dimeric forms. We find that bactericidal activity is lost against both Gram types as the deletion region increases, with the point at which this occurs varying between bacterial strains. The dimeric form of the peptides is more resistant to the peptide deletions, but this is not due just to increased charge. Our results indicate that the primary sequence, together with structure, is essential in the bactericidal action of this β-defensin derivative peptide and importantly identifies a short fragment from the peptide that is a potent bactericide

In-Situ Infrared Transmission Study of Rb- and K-Doped Fullerenes

We have measured the four IR active $C_{60}$ molecular vibrations in $M_{x}C_{60}$ $(M = K, Rb)$ as a function of doping $x$. We observe discontinuous changes in the vibrational spectra showing four distinct phases (presumably $x = 0, 3, 4$, and 6). The $1427cm^{-1}$ and $576cm^{-1}$ modes show the largest changes shifting downward in frequency in four steps as the doping increases. Several new very weak modes are visible in the $x=6$ phase and are possibly Raman modes becoming weakly optically active. We present quantitative fits of the data and calculate the electron-phonon coupling of the $1427cm^{-1}$ IR mode.Comment: 3 pages, Figure 1 included, 3 more figures available by request. REVTEX v3.0 IRC60DO

Far-infrared study of the Jahn-Teller distorted C60 monoanion in C60 tetraphenylphosphoniumiodide

We report high-resolution far-infrared transmission measurements on C(60)-tetraphenylphosphoniumiodide as a function of temperature. In the spectral region investigated (20-650 cm(-1)), we assign intramolecular modes of the C(60) monoanion and identify low-frequency combination modes. The well-known F(1u)(1) and F(1u)(2) modes are split into doublers at room temperature, indicating a D(5d) or D(3d) distorted ball. This result is consistent with a dynamic Jahn-Teller effect in the strong-coupling limit or with a static distortion stabilized by low-symmetry perturbations. The appearance of silent odd modes is in keeping with symmetry reduction of the hall, while activation of even modes is attributed to interband electron-phonon coupling and orientational disorder in the fulleride salt. Temperature dependences reveal a weak transition in the region 125-150 K in both C(60)(-) and counterion modes, indicating a bulk, rather than solely molecular, effect. Anomalous softening (with decreasing temperature) in several modes may correlate with the radial character of those vibrations. [S0163-1829(98)03245-7]

Observation and Assignment of Silent and Higher Order Vibrations in the Infrared Transmission of C60 Crystals

We report the measurement of infrared transmission of large C60 single crystals. The spectra exhibit a very rich structure with over 180 vibrational absorptions visible in the 100 - 4000 cm-1 range. Many silent modes are observed to have become weakly IR-active. We also observe a large number of higher order combination modes. The temperature (77K - 300K) and pressure (0 - 25KBar) dependencies of these modes were measured and are presented. Careful analysis of the IR spectra in conjunction with Raman scattering data showing second order modes and neutron scattering data, allow the selection of the 46 vibrational modes C60. We are able to fit *all* of the first and second order data seen in the present IR spectra and the previously published Raman data (~300 lines total), using these 46 modes and their group theory allowed second order combinations.Comment: REVTEX v3.0 in LaTeX. 12 pages. 8 Figures by request. c60lon