Interstate Vibronic Coupling Constants Between Electronic Excited States for Complex Molecules

In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular those where multiple electronic states are energetically closely lying and interact. As examples, we apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)$_3$(N,N)(L)]$^{n+}$ for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently.Comment: 36 pages, 7 figures, 4 table

The generalized differential quadrature method: study of vibrating thin circular arches

Los arcos circulares delgados constituyen un tema de permanente interés en el campo de la ingeniería estructural. En muchas de sus aplicaciones, el ingeniero de diseño necesita disponer de parámetros dinámicos que caractericen su comportamiento. En el presente trabajo se determinan las frecuencias naturales de los primeros modos normales de vibración en el plano, considerándose en el planteo tradicional los efectos de la inercia rotatoria así como también los de las deformaciones axiles de los arcos. Los extremos de los arcos se suponen elásticamente vinculados, sus desplazamientos en el plano están restringidos traslacional y rotacionalmente por dichos vínculos. De esta manera, es posible modelar como caso particular cualquier combinación de las clásicas condiciones de borde: libre, articulación, articulación deslizable, empotramiento. El Método de Cuadratura Diferencial Generalizado, GDQM su sigla en inglés, se elige para resolver el problema planteado. Este método se encuentra en un proceso de vigorosa revitalización según puede observarse en la literatura científica internacional actual. En el trabajo se realiza a su vez un análisis de las posibilidades del método, estudiando diferentes modelos discretos generados por diferentes densidades de mallas de puntos e incorporando la inclusión de puntos en los extremos. Se analiza tanto la velocidad de convergencia del método como su estabilidad numérica. Los resultados obtenidos se comparan, cuando es posible, con valores disponibles en la literatura, y también con valores calculados por los autores mediante el método de elementos finitos.Peer Reviewe

Lattice Expansion in Seamless Bi layer Graphene Constrictions at High Bias

Our understanding of sp2 carbon nanostructures is still emerging and is important for the development of high performance all carbon devices. For example, in terms of the structural behavior of graphene or bi-layer graphene at high bias, little to nothing is known. To this end we investigated bi-layer graphene constrictions with closed edges (seamless) at high bias using in situ atomic resolution transmission electron microscopy. We directly observe a highly localized anomalously large lattice expansion inside the constriction. Both the current density and lattice expansion increase as the bi-layer graphene constriction narrows. As the constriction width decreases below 10 nm, shortly before failure, the current density rises to 4 \cdot 109 A cm-2 and the constriction exhibits a lattice expansion with a uniaxial component showing an expansion approaching 5 % and an isotropic component showing an expansion exceeding 1 %. The origin of the lattice expansion is hard to fully ascribe to thermal expansion. Impact ionization is a process in which charge carriers transfer from bonding states to antibonding states thus weakening bonds. The altered character of C-C bonds by impact ionization could explain the anomalously large lattice expansion we observe in seamless bi-layer graphene constrictions. Moreover, impact ionization might also contribute to the observed anisotropy in the lattice expansion, although strain is probably the predominant factor.Comment: to appear in NanoLetter

Perturbation theory for plasmonic eigenvalues

We develop a perturbative approach for calculating, within the quasistatic approximation, the shift of surface resonances in response to a deformation of a dielectric volume. Our strategy is based on the conversion of the homogeneous system for the potential which determines the plasmonic eigenvalues into an inhomogeneous system for the potential's derivative with respect to the deformation strength, and on the exploitation of the corresponding compatibility condition. The resulting general expression for the first-order shift is verified for two explicitly solvable cases, and for a realistic example of a deformed nanosphere. It can be used for scanning the huge parameter space of possible shape fluctuations with only quite small computational effort

Probing the cosmic star formation using long Gamma-Ray Bursts: New constraints from the Spitzer Space Telescope

We report on IRAC-4.5mic, IRAC-8.0mic and MIPS-24mic deep observations of 16 Gamma-Ray Burst (GRBs) host galaxies performed with the Spitzer Space Telescope, and we investigate in the thermal infrared the presence of evolved stellar populations and dust-enshrouded star-forming activity associated with these objects. Our sample is derived from GRBs that were identified with sub-arcsec localization between 1997 and 2001, and only a very small fraction (~20%) of the targeted sources is detected down to f_4.5mic ~3.5microJy and f_24mic ~85microJy (3sigma). This likely argues against a population dominated by massive and strongly-starbursting (i.e., SFR > ~100 Msol/yr) galaxies as it has been recently suggested from submillimeter/radio and optical studies of similarly-selected GRB hosts. Furthermore we find evidence that some GRBs do not occur in the most infrared-luminous regions -- hence the most actively star-forming environments -- of their host galaxies. Should the GRB hosts be representative of all star-forming galaxies at high redshift, models of infrared galaxy evolution indicate that > ~50% of GRB hosts should have f_24mic > ~100microJy. Unless the identification of GRBs prior to 2001 was prone to strong selection effects biasing our sample against dusty galaxies, we infer in this context that the GRBs identified with the current techniques can not be directly used as unbiased probes of the global and integrated star formation history of the Universe.Comment: ApJ in press, 23 pages, 8 figures (scheduled for the ApJ 10 May 2006, v642 2 issue). Full resolution available at http://perceval.as.arizona.edu/~elefloch/Publis/ms_grb_spitzer.pd

The role of the maximum involvement of biopsy core in predicting outcome for patients treated with dose-escalated radiation therapy for prostate cancer

Abstract Purpose To evaluate the influence of the maximum involvement of biopsy core (MIBC) on outcome for prostate cancer patients treated with dose-escalated external beam radiotherapy (EBRT). Methods and materials The outcomes of 590 men with localized prostate cancer treated with EBRT (≥75 Gy) at a single institution were retrospectively analyzed. The influence of MIBC on freedom from biochemical failure (FFBF), freedom from metastasis (FFM), cause-specific survival (CSS), and overall survival (OS) was compared to other surrogates for biopsy tumor volume, including the percentage of positive biopsy cores (PPC) and the total percentage of cancer volume (PCV). Results MIBC correlated with PSA, T-stage, Gleason score, NCCN risk group, PPC, PCV, and treatment related factors. On univariate analysis, MIBC was prognostic for all endpoints except OS; with greatest impact in those with Gleason scores of 8–10. However, on multivariate analysis, MIBC was only prognostic for FFBF (hazard ratio [HR] 1.9, p = 0.008), but not for FFM (p = 0.19), CSS (p = 0.16), and OS (p = 0.99). Conclusions In patients undergoing dose-escalated EBRT, MIBC had the greatest influence in those with Gleason scores of 8–10 but provided no additional prognostic data as compared to PPC and PCV, which remain the preferable prognostic variables in this patient population.http://deepblue.lib.umich.edu/bitstream/2027.42/112858/1/13014_2012_Article_631.pd