Nuclear quantum effects in calculated NMR shieldings of benzene; a Feynman path integral study

The Feynman path integral Monte Carlo approach has been coupled to the gauge including atomic orbital formalism in order to analyse the absolute magnetic shieldings of the benzene nuclei under the conditions of thermal equilibrium. The Hamiltonian employed in the derivation of ensemble averaged NMR quantities is of the Hartree-Fock type. The basis set used is of 6–31G quality. The spatial delocalization of the atoms leads to a deshielding of both types of benzene nuclei relative to the shieldings experienced at the minimum of the potential energy surface. This deshielding has to be traced back to bond length elongations in thermal equilibrium. The influence of the nuclear fluctuations on the NMR parameters of benzene is quantum driven up to temperatures of 400 K; classical fluctuations are of minor importance in this low-temperature window.     

Main linac lattice design and optimization for Ecm=1 TeV CLIC

The Compact Linear Collider (CLIC) is a future e⁺e^- linear collider. The CLIC study concentrated on a design of center-of-mass energy of 3 TeV and demonstrated the feasibility of the technology. However, the physics also demands lower energy collision. To satisfy this, CLIC can be built in stages. The actual stages will depend on LHC results. Some specific scenarios of staged constructions have been shown in CLIC Concept Design Report (CDR). In this paper, we concentrate on the main linac lattice design for E_cm=1 TeV CLIC aiming to upgrade from E_cm=500 GeV CLIC and then to E_cm=3 TeV one. This main linac accelerates the electron or positron beam from 9 GeV to 500 GeV. A primary lattice design based on the 3 TeV CLIC main linac design and its optimization based on the beam dynamics study will be presented. As we use the same design principles as 3TeV CLIC main linac, this optimization is basically identical to the 3 TeV one. All the simulations results are obtained using the tracking code PLACET.     

Finite-difference schemes for scalar conservation laws with source terms

Explicit and semi-implicit finite-difference schemes approximatingnon-homogeneous scalar conservation laws are analyzed. Optimalerror bounds independent of the stiffness of the underlyingequation are presented. This author has been supported by The Norwegian Research Council(NFR), program No 100284/431. e-mail: schroll{at}igpm.rwth-aachen.de This author has been supported by The Norwegian Research Council(NFR), program Nos 100284/431 and STP.29643. e-mail: ragnar{at}ifi.uio.no     

Ground state and excited state properties of ethylene isomers studied by a combined Feynman path integral-ab initio approach

Ground state and excited state properties of ethylene, C₂H₄, and several ethylene isomers have been studied by Feynman path integral Monte Carlo (PIMC) simulations. The PIMC treatment of the atomic nuclei has been combined with different electronic Hamiltonians in order to analyse the influence of the nuclear degrees of freedom on electronic quantities. Electronic expectation values at the minimum of the potential energy surface (PES) have been compared with PIMC based ensemble averaged values. Ensemble averaged quantities have been derived by Hamiltonians of the ab initio type and a tight-binding (TB) one-electron model. The combined influence of anharmonicities in the interatomic potential and the quantum fluctuations of the atomic nuclei lead to ensemble averaged bondlengths r _g which are significantly larger than the parameters r _e, at the minimum of the PES. The implications of this bond length elongation for the electronic properties of ethylene are discussed. The occupied canonical molecular orbitals (CMOs) of ethylene are destabilized under the influence of the nuclear degrees of freedom while virtual CMOs are stabilized. These shifts of one-electron energies suggest a comparison of electronic excitation energies at the minimum of the PES with PIMC based ensemble averages. The quantum fluctuations of the nuclei cause a strong redistribution in the intensities of electronic transitions. Transitions, which are dipole allowed in the planar D_2h geometry of ethylene, lose intensity under the influence of nuclear quantum effects, and vice versa for electronic excitations that are dipole forbidden under D_2h symmetry. This ‘vibrational borrowing’ is enhanced with decreasing atomic masses. The Feynman centroid density has been used to calculate the anharmonic vibrational wavenumbers of C₂H₄ and C₂D₄. The results of the present PIMC simulations have been employed to emphasize general problems of electronic structure calculations based on a single nuclear configuration (i.e. the configuration at the minimum of the PES).     

SPECTROSCOPIC INVESTIGATION OF DIHYDRONICOTINAMIDES-I: CONFORMATION, ABSORPTION, AND FLUORESCENCE

Abstract— The 1(N)-(2,6-dichlorobenzyl)-1,4-dihydronicotinamide (I), N-methyl- and N,N-dimethyl-1(N)-(2,6-dichlorobenzyl)-1,4-dihydronicotinamide (II and III), respectively), and 1(N)-(2,6-dichloro-benzyl)-2-aminomethyl-1,4-dihydronicotinic acid lactame (IV) were synthesized as model compounds for natural coenzymes, and systematically studied by 1H NMR, UV/V1S absorption and fluorescence spectroscopy. The absorption at ∼ 340 nm argues for an effective conjugation between dihydropyridine and carboxamide π-system, and rules out any severely twisted conformation. For the natural coenzymes NADH and NMNH, as well as for I and II (with no or only one N-amide substituent), 1H NMR definitively establishes a transoid conformation in solution, with the carbonyl O close to 2-H of the dihydropyridine ring. N,N-dimethyl substitution effectively inverts the carboxamide orientation into the cisoid form. The 1H NMR data (as well as molar extinctions) for the fused-ring derivatives IV and V, with a fixed cisoid and transoid structure, respectively, provide final proof for the conformational assignment.
Absorption maxima are shifted to lower energies with increasing solvent polarity. In solvents which can act as hydrogen bond acceptors to the carboxamide N-H, absorption shows a general blue-shift of ∼ 10 nm. H-bond donor solvents do not affect absorption maxima but enhance molar extinction. Fluorescence maxima show a similar dependence on solvent polarity but no specific hydrogen-bonding effect. Fluorescence quantum yields appear increased tenfold in solvents donating H-bonds to the carboxamide C=O group. These results are interpreted in terms of the vinylogous amide resonance between C=O function and ring-N lone pair being the electronic interaction dominating in the ground state of dihydronicotinamides.     

Preliminary communication Multilayer light emitting diodes based on columnar discotics

Columnar discotics were used as the hole transporting layer in single layer, two layer and three layer light emitting diodes because of the unusually large hole mobility of such materials. The observations are that the onset fields are small compared with most devices using nondiscotic hole transporting layers, that these values are strongly reduced with increasing number of layers, that the orientation of the columns along the layer film normal causes a further decrease of the onset voltage and finally that the quantum efficiencies increase significantly as the number of layers is increased.     

SPECTROSCOPIC INVESTIGATION OF DIH YDRONICOTIN AMIDES-II. DIHYDRONICOTINAMIDE ADENINE DINUCLEOTIDE COMPLEXES WITH DEHYDROGENASES

Abstract— Detailed investigations are reported on absorption and fluorescence of dihydronicotinamide adenine dinucleotide in binary and ternary complexes with lactate dehydrogenase or malate dehydrogenase and substrates or substrate analogues. Polarity of the active site, as extracted from fluorescence maxima, reveals two types of dihydronicotinamide environment comparable to an aqueous and a dimethyl sulfoxide medium, respectively. Absorption maxima argue for absence of carboxamide/ acceptor hydrogen bonds in general. Vibrational fine structure in the absorption bands of some ternary complexes indicates the absence of carboxamide/donor hydrogen bonds. In these complexes, rotation of dihydronicotinamide within the binding site is established by means of fluorescence anisotropy decay.
These findings are interpreted in terms of the interaction between active site and dihydronicotinamide being highly specific for each individual complex. At the same time, they render any direct analogies between binding of reduced and oxidized coenzyme, and also between abortive and productive ternary complexes, highly problematical.