Detection of vibrational bending mode ν8 and overtone bands of the propargyl radical, HCCCH2 X̃ 2B1

Infrared (IR) absorption spectra of matrix-isolated HCCCH(2) have been measured. Propargyl radicals were generated in a supersonic pyrolysis nozzle, using a method similar to that described in a previous study (Jochnowitz, E. B.; Zhang, X.; Nimlos, M. R.; Varner, M. E.; Stanton, J. F.; Ellison, G. B. J. Phys. Chem. A 2005, 109, 3812-3821). Besides the nine vibrational modes observed in the previous study, this investigation detected the HCCCH(2) X? (2)B(1) out-of-plane bending mode (ν(8)) at 378.0 (±1.9) cm(-1) in a cryogenic argon matrix. This is the first experimental observation of ν(8) for the propargyl radical. In addition, seven overtone and combination bands have also been detected and assigned. Ab initio coupled-cluster anharmonic force field calculations were used to guide the analysis. Furthermore, ν(12), the HCCCH(2) in-plane bending mode, has been assigned to 333 (±10) cm(-1) based on the detection of its overtone (2ν(12), 667.7 ± 1.0 cm(-1)) and a possible combination band (ν(10) + ν(12), 1339.0 ± 0.8 cm(-1)). This is the first experimental estimation of ν(12) for the propargyl radical.     

The value of information to decision makers: an experimental approach using card-based decision gaming

This paper describes a novel experimental method for determining the value of different types of information to military decision makers. The experimental method used a simple scenario and a set of serials constructed from cards, each presenting a single piece of information and presented sequentially. Each of a number of pairs of players were taken through the scenario and asked to judge when they would make each of a pair of escalating responses to the situation. The data proved well suited to analysis using a probit model and is consistent with the hypothesis of a Bayesian decision mechanism with normally distributed ‘action points’. The methodology allowed the determination of weights for each of a number of different classes of information, together with estimates of the human and situational elements of variation, including estimates of the ‘prior belief’ of the different pairs of players.     

Nonadiabatic effects in the photoelectron spectrum of the pyrazolide-d3 anion: three-state interactions in the pyrazolyl-d3 radical

The 351.1 nm photoelectron spectrum of the 1-pyrazolide-d(3) anion has been measured. The photoelectron angular distributions indicate the presence of nearly degenerate electronic states of the 1-pyrazolyl-d(3) radical. Equation-of-motion ionization potential coupled-cluster singles and doubles (EOMIP-CCSD) calculations have been performed to study the low-lying electronic states. The calculations strongly suggest that three electronic states, energetically close to each other, are accessed in the photodetachment process. Strong interactions of the pseudo-Jahn-Teller type in each pair of the three states are evident in the calculations for the radical at the anion geometry. Model diabatic potentials of the three states have been constructed around the anion geometry in terms of the anion reduced normal coordinates up to the second order. An analytic method to parametrize the quadratic vibronic coupling (QVC) model potentials has been introduced. Parameters of the QVC model potentials have been determined from the EOMIP-CCSD and CCSD(T) calculations. Simulations of the 1-pyrazolide-d(3) spectrum have been performed with the model Hamiltonian, treating all vibronic interactions amongst the three states simultaneously. The simulation reproduces the fine structure of the observed spectrum very well, revealing complicated nonadiabatic effects in the low-lying states of the radical. The ground state of the 1-pyrazolyl-d(3) radical is (2)A(2) and the electron affinity is 2.935+/-0.006 eV. The first excited state is (2)B(1) with a term energy of 32+/-1 meV. While the high-symmetry (C(2v)) stationary points of the X (2)A(2) and A (2)B(1) states are minima, that of the state is a saddle point as a result of the pseudo-Jahn-Teller interactions with the other two states. The topology of the adiabatic potential energy surfaces is discussed.     

Tribasic integrals and identities of Rogers-Ramanujan type

Some integrals involving three bases are evaluated as infinite products using complex analysis. Many special cases of these integrals may be evaluated in another way to find infinite sum representations for these infinite products. The resulting identities are identities of Rogers-Ramanujan type. Some integer partition interpretations of these identities are given. Generalizations of the Rogers-Ramanujan type identities involving polynomials are given again as corollaries of integral evaluations.

     

Canonical orthonormalization and neglect of differential overlap

Löwdin's canonical orthonormalization procedure is non-unique if the overlap matrix has degenerate eigenvalues. A recent attempt by Roby to justify neglect of differential overlap is re-examined taking proper account of this lack of uniqueness. We conclude that his central result, eq. (6) in our paper, is formally correct in the limit of complete basis sets, but Roby's presentation lends a misleading interpretation to this equation. Consequently, some conclusions which are claimed to follow are, in fact, not valid. We briefly investigate the Roby approximation for finite basis sets and indicate the strengths and weaknesses when used for practical computations.     

A novel subshape molecular descriptor

Molecules with similar shapes and features often have similar biological activity. Several computational approaches search chemical databases for new leads or templates based on overall molecular shape similarity. However, active molecules often present critical subshapes that are required for binding, which may be missed by comparing overall shape similarity. We present a new approach to compare molecular shapes of different sizes and to calculate subshape similarity. We developed a skeletal representation of the shape which is topologically unrelated to covalent chemical connectivity. This simplifies rotational and translational sampling. We test initial possible alignments by matching similar triangles. This triangle-matching filter rapidly eliminates most geometrically impossible matches. Surviving matches are filtered further in successive stages. These stages involve direction, feature, and shape matching procedures. Our approach is applied to several situations demonstrating lead discovery and evolution.     

Comparison of algorithms and databases for matching unknown mass spectra

The most used algorithms for the identification of electron-ionization mass spectra are INCOS and probability based matching (PBM). For unknown spectra of high purity, ～75% of rank 1 answers are correct for both algorithms, matched against the National Institute of Standards and Technology 62,235 spectrum database. With matching criteria that retrieve 50% of the possible correct answers from the Wiley 228,998 spectrum database, 54% of the PBM and 42% of the INCOS answers are correct; for 85% purity unknowns, 48% and 27% are correct. For an unknown spectrum of two compounds, neither was reported in the first three INCOS answers; eight of the first ten PBM answers identify both components.     

The influence of surfaces and interfaces on coherent phonons in semiconductors

Experiments have shown that ultrafast optical excitation of semiconductors can produce oscillating changes in the optical properties of the material. The frequency of the oscillations in transmission or reflection usually matches one of the phonon modes, typically theq = 0 optical mode. These oscillations are known as coherent phonons. We discuss the role of surfaces and interfaces on the coherent phonon signal. We show that: (1) the coherent phonon signal can be used as a probe of the surface depletion field and (2) multiple interfaces as in a superlattice, can drastically alter the coherent phonon spectrum: screening of the modes in the superlattices is reduced and acoustic modes can now be excited.     

Acoustic scattering by benthic and planktonic shelled animals

Acoustic backscattering measurements and associated scattering modeling were recently conducted on a type of benthic shelled animal that has a spiral form of shell (Littorina littorea). Benthic and planktonic shelled animals with this shape occur on the seafloor and in the water column, respectively, and can be a significant source of acoustic scattering in the ocean. Modeling of the scattering properties allows reverberation predictions to be made for sonar performance predictions as well as for detection and classification of animals for biological and ecological applications. The studies involved measurements over the frequency range 24 kHz to 1 MHz and all angles of orientation in as small as 1 degree increments. This substantial data set is quite revealing of the physics of the acoustic scattering by these complex shelled bodies and served as a basis for the modeling. Specifically, the resonance structure of the scattering was strongly dependent upon angle of orientation and could be traced to various types of rays (e.g., subsonic Lamb waves and rays entering the opercular opening). The data are analyzed in both the frequency and time domain (compressed pulse processing) so that dominant scattering mechanisms could be identified. Given the complexity of the animal body (irregular elastic shell with discontinuities), approximate scattering models are used with only the dominant scattering properties retained. Two models are applied to the data, both approximating the body as a deformed sphere: (1) an averaged form of the exact modal-series-based solution for the spherical shell, which is used to estimate the backscattering by a deformed shell averaged over all angles of orientation, and produces reasonably accurate predictions over all k1a(esr) (k1 is the acoustic wave number of the surrounding water and a(esr) is the equivalent spherical radius of the body), and (2) a ray-based formula which is used to estimate the scattering at fixed angle of orientation, but only for high k1a(esr). The ray-based model is an extension of a model recently developed for the shelled zooplankton Limacina retroversa that has a shape similar to that of the Littorina littorea but swims through the water [Stanton et al., J. Acoust. Soc. Am. 103, 236-253 (1998b)]. Applications of remote detection and classification of the seafloor and water column in the presence of shelled animals are discussed.