bluuebunny/crossref_metadata_2025_split huggingface dataset:
A. Experiment and Theory of High Resolution Spectra of Rovibronic Molecular States. Improved Theoretical 1Σu+ and 1Πu Wavefunctions, Energies, and Transition Moments for the H2 Molecule
Authors: Dressler K. , Wolniewicz L. 
Published: September 2013

AbstractIn the emission spectrum of molecular hydrogen the Rydberg‐Rydberg bands of type nsσg−2pσu,πu are an order of magnitude weaker than the corresponding bands with ndσg upper states. We have calculated the dipole moment functions for the electronic 1Σg+ − 1Σu+ and 1Σg+ ‐ 1Πu transitions whose upper states at small inter‐nuclear distances are of 2s, 3s, 3dσ, 4s, and 4dσ character, with lower states 2pσB, 3pσ B', 4pσ B” 1Σu+, 2pπ C, and 3pπ D 1Πu. The results confirm that the transitions of s–p character are much weaker than the d‐p ones. We have also obtained improved Born‐Oppenheimer electronic energy curves and adiabatic energy corrections for the lowest four 1Σu+ and two 1Πu states, and nonadiabatic coupling functions among the four 1Σu+ states. In the B 1Σu+ state the theoretical term values of the lowest rovibronic levels agree, after correction for nonadiabatic and relativistic energy shifts, with spectroscopic measurements in H2 and D2 within the combined uncertainties of the experiments and of the small, unknown radiative energy corrections.
Dipole Moment Function of Methane and Analytical Anharmonic, 9‐dimensional Potential Surface: Theory and Experiment for the Permanent Electric Dipole Moment of CH2D2 Using Quantum Monte Carlo Calculations and FIR Spectroscopy
Authors: Hollenstein Hans , Marquardt Roberto R. , Quack Martin , Suhm Martin A. 
Published: September 2013

AbstractThe pure rotational spectrum in the far‐infrared and its absolute intensity in the vibrational ground state of CH2D2 and CHD3 were measured by high‐resolution interferometric Fourier transform techniques. The analysis of the integrated absorption cross sections results in a permanent, vibrationally induced electric dipole moment |μ0| = (8.6 ± 1.4)·10−3 Debye for CH2D2. This value is much more reliable than the older value existing in the literature and is also in much better agreement with our previously published theoretical estimate (μ0 = ‐(7.60±0.50)·10−3 Debye, the z‐axis being the C2 axis with sign chosen such that the H‐atoms have positive z‐coordinates).
The Vibrational Spectrum of Fluorochloroethyne FCCC1: Ab Initio Calculations and High Resolution Infrared Studies
Authors: Breidung J. , Bürger H. , Senzlober M. , Thiel W. 
Published: September 2013

AbstractThe FCCC1 molecule has been studied by ab initio methods and high resolution IR spectroscopy. Employing a TZ2Pf basis set the quadratic, cubic, and quartic force fields have been determined at the SCF and MP2 levels, and the equilibrium structure has been calculated. The vibrational and rovibrational parameters deduced from the force fields have guided the analysis of high resolution FTIR spectra of FCCC1 in the v1, v2, 2v4 and v4 v5 regions. Therefrom, ground, v4 = 1 and v5 = 1 rotational parameters have been determined by means of lower state combination differences. The 2v4 (Σ+) and v4v5 (Σ+ and Δ) levels have been analyzed in detail, and anharmonic perturbations disclosed with the help of the ab initio results. The available experimental data are in excellent agreement with the ab initio predictions.
C. Spectroscopy of Excited States, Kinetics and Photodissociation. Fine Structure and Hyperfine Structure Effects in Unimolecular and Complex‐Forming Bimolecular Reactions
Authors: Troe J. 
Published: September 2013

AbstractFine structure and hyperfine structure effects can influence the kinetics of unimolecular and complex‐forming bimolecular reactions. The corresponding energetic effects are analyzed in the framework of the statistical adiabatic channel model (SACM). The reactions O+OH → O2 + H, OH + CO → H + CO2, C+ + OH → products, C+ + NO → products, and NO2 → O + NO serve as examples.
Vibration to Electronic Energy Transfer in Carbon Monoxide between X1Σ and a3Π
Authors: Schulz O. , Lin J. X. , Urban W. 
Published: September 2013

AbstractA careful analysis of experimental data for a CO laser plasma shows a considerable depletion of the vibrational distribution of the electronic ground state in the energy range of the first excited electronic state a3Π. If the transferred population would reappear completely, the corresponding concentration of CO in the a3Π state should be observable by the most sensitive Faraday laser magnetic resonance technique. From the fact that no signal could be found, we deduce an upper concentration for CO a3Π which is then compared to a new refined model. This model takes into account both VE transfer rates between the ground state and the a3Π and a relaxation rate for the triplet state.
Vibrational IR‐Multiphoton Excitation of Thiirane‐1‐oxide (C2H4SO) and d‐Thiirane‐1‐oxide (C2H3DSO)
Authors: Gross Heike , He Yabai , Jeitziner Christian , Quack Martin , Seyfang Georg 
Published: September 2013

AbstractWe report the IR‐laser‐induced dissociation of C2H4SO and of C2H3DSO, which was synthesized for the first time. After multiphoton excitation in the frequency range of the SO chromophore (with a large band strength of G = 2.4 pm2 for C2H4SO and 2.8 pm2 for C2H3DSO) in the 1060‐1090 cm−1 range of the CO2 laser the product analysis was carried out by static yield measurements using quantitative IR‐spectroscopy of ethylene (C2H3D, C2H4). Effective laser chemical rate constants k1(st) = (0.70±0.38) cm2 J−1 for C2H3DSO with excitation at v̄(R28) = 1083.48 cm−1 and (0.52±0.14) cm2 J−1 for C2H4SO were obtained from a fit to the fluence dependence of the photochemical primary yields. A nonlinear intensity dependence of the apparent product yield (Papp) was found by using different temporal pulse profiles (singlemode, mode‐locked and multimode pulses) at 1083.48 cm−1 (9R28) for C2H4SO and at 1082.30 cm−1 (9R26) for C2H3DSO in static yield measurements and time‐resolved experiments. FTIR measurements were performed to assign the fundamentals of C2H3DSO, which are compared with the harmonic frequencies calculated using GAUSSIAN 92 at MP2 level with different basis sets.
Ultrafast Collisional Redistribution of Vibrational Energy in Highly Excited Polyatomic Molecules. The Role of Intramolecular Interactions
Authors: Kosterev A. A. , Malinovsky A. L. , Tretyak S. A. , Ryabov E. A. 
Published: September 2013

AbstractTime‐resolved Raman probing technique is used to investigate the collisional relaxation of high‐lying C‐H vibrations in CHF3 and CHF2Cl molecules. The relaxation rates both in collisions with parent molecules and a number of buffer gases were measured. The rate values were found to be abnormally fast. The relaxation is faster than single collision in parent gas and requires a few (3‐8) collisions for nonpolar gases. For polar gases the relaxation is still faster.The conclusion is made that observed ultrafast relaxation of C–H modes is caused by energy transfer from excited “bright” states to nearby “dark” ones. Possible mechanisms of the above transfer are discussed.
Photodissociation of the HCO+ Ion
Authors: Koch A. , van Dishoeck Ewine F. , van Hemert M. C. 
Published: September 2013

AbstractAb initio MRD‐CI calculations are presented for the photodissociation of the HCO+ ion, which plays an important role in the chemistry in interstellar space and in combustion flames. One‐dimensional potential energy curves along the C‐H bond length coordinate are presented for the lowest eight electronic singlet states. The calculations show that the 11Π state is the lowest excited state through which dissociation is possible and which can be reached by dipole‐allowed transitions. The photodissociation dynamics on the 11Π potential and through the higher‐lying 2 and 31Σ+ states are studied in the one‐dimensional approximation, using a time‐independent quantum mechanical treatment. The geometry dependence of the electric dipole transition moment is taken into account.
D. New Experimental Methods and Applications. Applications of Fluorescence Demodulation Spectroscopy (FDS)
Authors: Klein Uwe K. A. 
Published: September 2013

AbstractSome possibilities of fluorescence demodulation spectroscopy (FDS) are discussed. These include the application to decay in the nanosecond to picosecond range and to transitions in spectra with a resolution of less than the Doppler width, i.e. to high‐resolution spectroscopy. Also, a variation of FDS, i.e. demodulation spectroscopy (DS) for use in femtosecond ‐ kinetics, allowing the investigation of ultrashort‐lived transition states, is being discussed.
Recent Advances in Rovibrationally Resolved FTIR Supersonic Jet Spectroscopy of Transients, Weakly Bound Dimers and Trimers
Authors: Hartz C. L. , Wofford B. A. , McIntosh A. L. , Meads R. F. , Lucchese R. R. , Bevan J. W. 
Published: September 2013

AbstractRecent advances in the development and application of a highly sensitive near infrared FTIR supersonic jet spectrometer are reported. Investigations of: v1 OC‐HF; ν1, ν2 OC‐HCl; ν1 +, ν2 ± (HCl)2; ν1, ν1±ν21 Ar‐HCl and ν1 N2‐HCl will be presented. In specific cases, a direct comparison with corresponding spectra recorded using tunable near infrared laser supersonic jet and molecular beam absorption spectrometers will be made to illustrate the current capabilities and limitations of the FTIR supersonic jet spectrometer. As an example of the application of the technique to clusters, we report a study of the ν5 HCl asymmetric stretching band in the trimer, (HCl)3. Some preliminary studies of discharge‐generated species will also be reported using the jet spectrometer. The latter include: i) the investigation of vibrational hot bands in CO and ii) A2Π3/2,1/2→X2Σ+ rovibronic transitions in the CN radical.
Ab Initio Calculations of the Binding Energies of Small (H2O)n Clusters (n = 1…4)
Authors: Klopper Wim , Schütz Martin 
Published: September 2013

AbstractThe binding energies of the water dimer, trimer, and tetramer were calculated employing coupled‐cluster theory with singles, doubles, and non‐iterative triples (CCSD(TT)), and Møller‐Plesset second‐order perturbation theory (MP2) with terms linear in the interelectronic coordinates (MP2‐R12). Various atomic orbital (AO) basis sets were used to investigate the convergence of the binding energy towards the AO basis set limit. The calculations were performed at fixed geometries taken from the literature (which are geometries that were optimized at the MP2 level). Binding energies (De) of 20.9 kJ/mol (dimer), 69.2 kJ/mol (trimer), and 123.8 kJ/mol (tetramer) were obtained from MP2‐R12 calculations with a large 7s5p3d1f/5s3p1d AO basis set. These values are supposed to be very close (with errors of 2–5%) to the AO basis set limit. Binding energies obtained from CCSD(T) and MP2 calculations with the aug‐cc‐pVDZ basis set agreed within 3%. Hence, the MP2 level of calculation appeared to be appropriate to describe hydrogen‐bonding in small water clusters. All calculations were corrected for the basis set superposition error (BSSE) by the full counterpoise method.
A Pump & Dump & Probe Strategy for the Spectroscopy of the Transition State During a Laser‐Controlled Isomerization: Model Simulation for the Cope Rearrangement of 2,6‐Dicyanoethylmethylsemibullvalene
Authors: Dohle M. , Manz J. , Paramonov G. K. 
Published: September 2013

AbstractOur previous strategy for laser control of isomerization by intense ultrashort (ps) infrared laser pulses is extended to the spectroscopy of the transition state during the laser‐driven chemical reaction, by means of a pump & dump & probe approach. The pump laser pulse excites a reactant state, typically the ground state, to a delocalized “transition state” with energy just above the shallow potential barrier which separates the potential wells of two near‐degenerate isomers. The dump laser pulse de‐excites the transition state to a product state, e.g. its ground state. The transient population of the transition state is monitored by another ultrashort, yet weak probe laser pulse which induces the electronic transition to the vibrational ground state of the next accessible excited electronic state. The strategy is demonstrated by a simple model simulation of the laser‐driven Cope rearrangement of 2,6‐Dicyanoethylmethylsemibullvalene (DEM‐SBV) by means of representative time‐dependent wave‐packets. This example is used for a discussion of the new pump & dumb & probe method.
Toward Laser Control of Molecular Motion
Authors: Letokhov V. S. 
Published: September 2013

AbstractThis paper considers the possibilities of extending to molecules the laser methods of controlling the motion of atoms. Techniques are analyzed involving the cyclic interaction between the laser field and the molecule at two energy levels by stimulated quantum transitions alone. The use of the sympathetic cooling technique is suggested for molecular ions, this potentially enabling one to obtain extremely narrow spectral lines suitable for the detection of the splitting of energy levels in molecular enantiomers due to parity violation.
The Effect of the Torsional Barrier Height on the Acceleration of Intramolecular Vibrational Relaxation (IVR) by Molecular Flexibility
Authors: Perry David S. , Bethardy G. A. , Wang Xiaoliang 
Published: September 2013

AbstractPrevious work by the present authors (Can. J. Chem. 72, 652 (1994)) pointed out the acceleration of IVR in flexible molecules when the prepared vibration is close to the centre of flexibility (COF). A COF was defined as a bond about which hindered internal rotation can occur thereby giving rise to molecular flexibility. Here, it is shown that the rate of IVR is inversely correlated with the height of the barrier to internal rotation for systems in which the prepared vibration is adjacent to the COF. In ethanol and hydrogen peroxide the barriers are low (≈︁ 380 cm−1) and the relaxation of the adjacent O‐H vibration is fast (4 to 26 ps). On the other hand, higher barrier torsions (1100 to 1700 cm−1) adjacent to the chromophore in 1–butyne, 2‐fluoroethanol, and 1,2‐di‐fluoroethane give rise to much longer IVR lifetimes (270 to 565 ps).Most of the IVR lifetimes used in this paper were derived from discretely resolved spectra in which a bright state transition is fragmented into a clump of molecular eigenstates; the remainder are from rotationally selected double resonance spectra. An algorithm is described for the derivation of consistent IVR lifetimes for coupling cases ranging from intermediate down to the very sparse limit where only a few perturbing states are explicitly observed in the spectrum.
Highly Vibrationally Excited Non Rigid Molecules: Overtone Spectroscopy and Intramolecular Dynamics of Gaseous Nitromethane
Authors: Cavagnat D. , Lespade L. , Lapouge C. 
Published: September 2013

AbstractThe CH stretching overtone spectra of gaseous nitromethane NO2CH3 (Δv = 4 to 6) and of its monohydrogenated derivative NO2CHD2 (Δv = 2 to 6) have been recorded and analysed with a theoretical treatment which takes into account the coupling of the CH stretch with the low hindered internal rotation of the methyl group and with isoenergetic combination states by Fermi resonance. The calculated spectra reproduce well the experimental ones.
Reinvestigation of the 2v1 Band in Trifluoropropyne using a Frequency Stabilized 1.5 μm Color Center Laser in Conjunction with a Laser Field Build‐up Cavity
Authors: Gambogi Joan E. , Becucci Maurizio , O'Brien Christopher J. , Lehmann Kevin K. , Scoles Giacinto 
Published: September 2013

AbstractThe highly perturbed spectrum of the first overtone of the acetylenic CH stretch in trifluoropropyne has been reinvestigated with an improved multi‐laser, optothermal detection, molecular beam spectrometer. The modifications include installing a build‐up cavity to enhance the coupling between a 1.5 μm color center laser and the molecular beam, and stabilizing the laser frequency to improve the spectrometer's resolution. Upon injecting 25 mW into the cavity, a power enhancement of about 600 is measured. The laser frequency is stabilized by locking it to an external, temperature stabilized, etalon and applying the feedback to an intracavity electro‐optic crystal. The frequency stability reached is estimated to be less than 4 parts in 1010 or 75 kHz (in a 30 Hz bandwidth centered at 300 Hz).Utilizing infrared/infrared double resonance, the K components of this highly perturbed spetrum were assigned. The results indicate that the lifetime of the acetylenic CH stretch is approximately 1.4 ns and does not change as a function of J' for 0 ≤ J' ≤4. In agreement with a previous lower resolution study [J. Chem. Phys. 95, 3891 (1991)], the P(1) clump shows an experimental density of states almost equal to the calculated one and the level spacing distribution is similar to that of a Gaussian Orthogonal Ensemble indicating chaotic classical dynamics.
The Acetylene S0 Surface: From Dispersed Fluorescence Spectra to Polyads to Dynamics
Authors: Solina Stephani Ann B. , O'Brien Jonathan P. , Field Robert W. , Polik William F. 
Published: September 2013

AbstractDispersed Fluorescence spectra of acetylene have been recorded and unzipped, through a fortuitous coincidence of FC active modes and active anharmonic resonances, there by pictorially revealing the key factors controlling the vibrational dynamics on the acetylene S0 surface. When energy is placed into very high excitation of the trans‐bend and moderate excitation of the CC stretch, three approximately conserved quantities survive, i.e., no trace of the expected total breakdown of vibrational constants of motion due to energetic access to the vinylidene isomer is observed for vibrational energies up to at least 16400 cm−1. Unzipping the DF spectrum reveals the FC intensity profiles for the acetylene Ã ↔ X̃ system with two FC active modes. Also, the unzipped DF spectrum clearly demonstrates that IVR increases within a polyad by increasing trans‐bead, v4, and by decreasing CC stretch, v2. Increasing IVR with increasing v4 or decreasing v2, are both cases where the first few resonance tiers play the dominant role in controlling IVR for the initial states prepared in these experiments, very high excitation in the trans‐bend and moderate excitation in the CC stretch.
Localization of Vibrational Excitation: A Simple Model
Authors: Schmid G. M. , Silbey R. J. 
Published: September 2013

AbstractA simple model of localization of vibrational excitation in molecules is presented which is based on the idea to treat the dynamics of the molecular equilibrium configuration and the molecular oscillations around it as different degrees of freedom. From the comparison of their timescales, two limiting regimes are identified where localization occurs under formation of quasiparticles: the standard “local mode limit” and a previously undiscussed limit.
Morbidity in survivors of child and adolescent meningioma
Authors: Kotecha Rishi S. , Jacoby Peter , Cole Catherine H. , Gottardo Nicholas G. 
Published: September 2013

BACKGROUNDThe extent of initial surgical resection has been identified as the strongest prognostic indicator for survival in child and adolescent meningioma. Given the paucity of data concerning long‐term outcome, the authors undertook a meta‐analysis to analyze morbidity in survivors of this disease.METHODSIndividual patient data were obtained from 19 case series published over the last 23 years through direct communication with the authors. Ordinal logistic regression models were used to assess the influence of risk factors on morbidity.RESULTSOf 261 patients, 48% reported a completely normal life with no morbidity, and 25% had moderate/severe meningioma‐associated morbidity at last follow‐up. Multivariate analysis identified relapse as the only independent variable associated with an increased risk of morbidity (odds ratio, 4.02; 95% confidence interval, 2.11‐7.65; P ≤ .001). Univariate analysis also revealed an increased risk for patients with neurofibromatosis (odds ratio, 1.90; 95% confidence interval, 1.04‐3.48; P = .04). Subgroup analysis identified a higher incidence of morbidity among patients who had intracranial tumors with a skull base location compared with a nonskull base location (P ≤ .001). Timing at which morbidity occurred was available for 70 patients, with persistence of preoperative tumor‐related symptoms in 67% and as a result of therapy in 20%.CONCLUSIONSThe majority of survivors of child and adolescent meningioma had no or only mild long‐term morbidity, whereas 25% had moderate/severe morbidity, with a significantly increased risk in patients with relapsed disease. In the majority, morbidity occurred as a consequence of the tumor itself, justifying aggressive surgery to achieve gross total resection. However, for patients with neurofibromatosis and skull base meningioma, a more cautious surgical approach should be reserved. Cancer 2013;119:4350–4357. © 2013 The Authors. Cancer published by Wiley Periodicals, Inc. on behalf of the American Cancer Society.
Energy transfer induced enhancement of localized exciton emission in ZnO nanoparticle–anthracene hybrid films
Authors: Main Kyle , Shimada Ryoko , Fujita Yasuhisa , Neogi Arup 
Published: September 2013

AbstractOptically transparent and high‐quality hybrid ZnO nanoparticle and anthracene embedded polyphenylsiloxane (PPS) glass films were spin‐coated on quartz substrates. A strong Förster resonant energy transfer (FRET) process was indicated by the observation of quenching of the ZnO emission and an enhancement of the anthracene emission at room temperature. The efficiency of this energy transfer between ZnO and the S1 vibronic states of the anthracene molecules can be optimized to exceed 90%.magnified imageVisible emission from anthracene only, ZnO only, and the ZnO/anthracene hybrid. The anthracene emission is visibly more intense in the presence of ZnO.(© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Alternatives to key factor analyses for assessing the population dynamics of Hypera postica (Coleoptera: Curculionidae)
Authors: Zahiri Babak , Fathipour Yaghoub , Khanjani Mohammad , Moharramipour Saeid , Zalucki Myron Philip 
Published: September 2013

AbstractKey factors are those causes that are most responsible for the observed changes in population density between generations. Stage‐frequency of alfalfa weevil was modeled using Manly‐1997 model. Multiple decrement life table parameters from an 8 year‐field study were analyzed using traditional and λ contribution methods. In traditional method, the key factor was determined as kLII, the death of period‐two larvae from all mortality factors, whereas in λ contribution method, the key factor was determined as b2&3, oviposition rate of females per square meter. These differences result directly from the sensitivity of the population growth rate, λ, to variation of both k and b in various stages of the weevil. Among all mortality factors, only kLI‐Z, the death of period‐one larvae from the entomopathogenic fungus, Zoophthora phytonomi (Arthur) Batko (Zygomycetes: Entomophthoraceae), kLII and kLII‐Z, the death of period‐two larvae from Z. phytonomi, acted in a density dependent fashion. Remaining factors were independent of population densities affected. Using λ contribution method, life table approach still remains a major way of studying the dynamics of field populations for applied ecologists and population managers.
Positionen zivilgesellschaftlicher Akteure und von Parteien zu Wettbewerb im Gesundheitswesen
Authors: Brünger Martin , Grube Maike , Buttmann Nina 
Published: September 2013

Einleitung
Eine zentrale Rolle in der gesundheitspolitischen Auseinandersetzung spielen Ausmaß und Ausgestaltung des Wettbewerbs im Gesundheitssystem. Schwerpunkt dieses Artikels ist die Darstellung der unterschiedlichen Standpunkte von Parteien und zivilgesellschaftlichen Akteuren zum Systemwettbewerb zwischen Gesetzlicher (GKV) und Privater Krankenversicherung (PKV) im dualen Krankenversicherungssystem.