Two-dimensional vibrational lineshapes of amide III, II, I and A bands in a helical peptide

An effective exciton Hamiltonian for all amide bands is used to calculate the absorption and photon echo spectra of a 17 residue helical peptide (YKKKH17). The cross peak bandshapes are sensitive to the inter-band couplings. Fluctuations of the local amide frequencies of the all amide fundamental and their overtone and combination states are calculated using the multipole electric field induced by environment employing the electrostatic DFT map of N-methyl acetamide. Couplings between neighboring peptide units are obtained using the anharmonic vibrational Hamiltonian of glycine dipeptide (GLDP) at the BPW91/6-31G(d,p) level. Electrostatic couplings between non-neighboring units are calculated by a fourth rank transition multipole coupling (TMC) expansion including 1/R³ (dipole–dipole), 1/R⁴ (quadrupole–dipole), and 1/R⁵ (quadrupole–quadrupole and octapole–dipole) interactions.     

Damping of the giant dipole resonance in hot,strongly rotating nuclei

The isovector dipole density-density response of hot rotating nuclei is calculated applying a cranked deformed Nilsson potential together with a separable dipole-dipole residual interaction. The transformation of the response function from the internal rotating coordinate frame to the laboratory frame is discussed and illustrated by classical results for a charged particle moving in a harmonic-oscillator potential. Calculations for ¹⁰⁸Sn, ¹⁵²Dy and ¹⁹⁶Pb are presented. For ¹⁰⁸Sn at high excitation energy thermal fluctuations of the shape gives rise to a rather structureless strength function with a considerable width. For ¹⁵²Dy and ¹⁹⁶Pb superdeformed minima of the potential surface are predicted. The coupling of the giant dipole resonance to the shape degrees of freedom of superdeformed nuclei can split the vibration by ≈ 10 MeV, the lowest peak being expected at an excitation energy of ≈ 7–8 MeV and carrying ≈ 30% of the energy-weighted sum rule.     

Formulae which relate pressure,activity and potentials of mean force to sums of integrals over Ursell-Mayer correlation functions of the distribution functions

The pure rotational spectrum in the far-infrared between 30 and 170 cm^-1 and its absolute intensity has been measured for CH₂D₂ in the vibrational ground state by high-resolution interferometric Fourier transform techniques. The analysis of the integrated cross-sections in the essentially water-free spectrum results in an accurate value for the permanent, vibrationally induced ground state electric dipole moment of CH₂D₂|μ₀| = (6·40±0·33) x 10^-3D.The influence of centrifugal effects on intensities and on the determination of the permanent dipole moment was investigated. Although centrifugal effects are important for the explanation of single band profiles, they appear to be of little relevance for the resulting permanent dipole moment. A new, more general 9- dimensional dipole moment function for methane is derived from ab initio calculations and experimental band strength information of CHD₃. Quantum Monte Carlo calculations using this function and a new, more general 9- dimensional analytical, anharmonic potential function for methane yield a semi-theoretical estimate μ₀ ^z = – (7·8±0·5)x10^-3D for CH₂D₂.     

Low-energy e4 compton scattering of spin-12 targets without C,P and T invariances

We have studied the low-energy e⁴ Compton scattering on $\text{spin}\text{-}\text{1}\text{2}$ targets without assuming C, P and T invariances. It is shown that the scattering amplitude has a term ω³ ln ω (ω is the energy of incident photon in the lab frame), whose coefficient is determined entirely by the charge, mass, magnetic dipole moment, and electric dipole moment of the target. To derive the result, we calculate the second-order (in ω) terms of the e² Compton scattering amplitudes. When the electric dipole moment (whose existence violates P and T but conserves PT) is set to zero, the result reduces to that obtained before by Lin assuming C, P and T invariances.     

Experimental Determination of Ground and Excited State Dipole Moments of N,N-Bis (2, 5-di-tert-butylphenyl)-3, 4:9, 10-perylenebis (dicarboximide) (DBPI) A Photostable Laser Dye

In the present work, the absorption, emission spectra and dipole moments(μ_g, μ_e) of N, N-bis (2, 5-di-tert-butylphenyl)-3, 4:9, 10- perylenebis (dicarboximide) (DBPI) have been studied in solvents of various polarities at room temperature. Using the methods of solvatochromism, the difference between the first excited singlet state (μ_e) and ground state (μ_g) dipole moments was estimated from Lippert – Mataga,, Bakhshiev, Kawski – Chamma – Viallet equations. The change in dipole moment (Δμ) was also calculated using the variation of the Stokes shift with microscopic solvent polarity parameter (E _T ^N ). It was observed that the value of excited singlet state dipole moment is higher (3.53 Debye) than the ground state one (1.92Debye), showing that the excited state of DBPI is more polar than the ground state.     

The search for a potentially new molecular species,SiAs: A theoretical contribution

Electronic states of a new molecular species, SiAs, correlating with the three lowest dissociation channels are characterized at a high-level of theory using the CASSCF/MRCI approach along with quintuple-ξ quality basis sets. This characterization includes potential energy curves, vibrational energy levels, spectroscopic parameters, dipole and transition dipole moment functions, transition probabilities, and radiative lifetimes. For the ground state (X²Π), an assessment of spin–orbit effects and the interaction with the close-lying A²Σ⁺ state is also reported. Similarities and differences with other isovalent species such as SiP and CAs are also discussed.     

Infrared spectra of thin films of α-crystalline hexafluoroethane: a manifestation of resonant dipole–dipole interaction in the range of fundamental vibrational modes ν<Subscript>5</Subscript> and ν<Subscript>10</Subscript>

Infrared reflection-absorption spectra of thin films of α-crystalline hexafluoroethane deposited on a gold-plated copper mirror are measured at temperatures of 70 and 80 K. The bands corresponding to strong in the dipole absorption vibrations ν₅ and ν₁₀ have complex contours, the shape of which is explained in terms of the resonant dipole–dipole interaction between identical spectrally active molecules of the crystal. Splittings of the complex ν5 and ν10 bands are explained taking into account two effects: the Davydov splitting and the LO–TO splitting of the strong modes. Bands of the asymmetric ¹³С¹²СF₆ isotopologue in the absorption spectrum of the crystal exhibit an anomalously large isotope shift as compared with the shift in the spectrum of free molecules. This anomaly is explained by intermolecular resonant dipole–dipole interaction of asymmetric ¹³С¹²СF₆ isotopologue with molecules of the environment, consisting of the most abundant ¹²C₂F₆ isotopologue. The correctness of the given interpretation is confirmed calculating these three effects in the model of resonant dipole–dipole interaction.     

11Li,14Be和17B核的软偶极共振模式

假定¹¹Li,¹⁴Be和¹⁷B核是由核芯和两个外层中子所组成,用Sum Rule探讨这类核的巨偶极共振,给出软偶极共振的能量和强度。结果与其它理论计算进行了比较。 关键词：     

Coupled-channel description of the photodisintegration of 24Mg, 28Si, and 32S nuclei within the intermediate-coupling scheme

The coupled-channel method is used to calculate photonuclear reactions on ²⁴Mg, ²⁸Si, and ³²S nuclei within the intermediate-coupling scheme. The origin of relatively narrow peaks corresponding to photoabsorption on these nuclei is studied. Partial channels of giant-dipole-resonance decay are considered. It is shown that the splitting of the giant dipole resonance in the ²⁴Mg nucleus into two broad maxima is due to the deformation of its surface.     

Analog giant dipole excitation in Si(n,p) at 59.6 MeV

The parent analog of the giant dipole resonance in ²⁸Si is studied by means of the (n, p) reaction. The continuum contribution to the giant dipole region was estimated by a phenomenological parameterization. The observed cross section exhausts 31% of the SJ sum rule; 88% of the GT sum rule or 67% of the Myers-Swiatecki prediction. A comparison is made to the giant resonance region observed in the ²⁸Si(p, p') reaction which was recently used, via comparison to ²⁸Si(α, α'), to infer that the GDR in ²⁸Si is not excited or at least not seen in (p, p').     

LCAO-MO Calculation of Dipole Transition Moment of Some First-Row Transition Metal Tetroxy Anions

Abstract

Recently very encouraging results of semiempirical parameteric calculation of dipole transition moments of the lowest energy t₁ ? 2e (¹A₁ - ¹T₂) transition of permanganate and chromate ions have been reported. In the case of vanadate ion, which is isoelectronic with the permanganate and chromate ion, no such study of spectral intensities appears to have been reported so far. A parameteric calculation in terms of a single parameter β, the ligand mixing coefficient using Richardson's orbitals⁴ and both dipole velocity and dipole length operators have been reported in the present paper.     

Photodisintegration of Light Nuclei

The first microscopic calculation of inelastic reactions on nuclei with mass number A = 6 is presented. In particular, we consider the total photoabsorption cross section of ⁶He and ⁶Li. It is shown that the halo nucleus ⁶He exhibits two types of dipole resonances, the normal giant dipole resonance and a low-energy soft dipole resonance associated with the excitation of the outer neutrons. Comparing our results with available experimental data we note the role of P-wave interaction. Calculations are performed using the Lorentz integral transform (LIT) method and the effective interaction in the hyperspherical harmonics formalism (EIHH).     

1H relaxation and dynamics of triphenylbismuth in deuterated solvents

ABSTRACT

¹H spin–lattice relaxation experiments have been performed for triphenylbismuth dissolved in fully deuterated glycerol and tetrahydrofuran. The experiments have been carried out in a broad frequency range, from 10?kHz to 40?MHz, versus temperature. The data have been analysed in terms of a relaxation model including two relaxation pathways: ¹H-¹H dipole–dipole interactions between intrinsic protons of triphenylbismuth molecule and ¹H-²H dipole–dipole interactions between the solvent and solute molecules. As a result of the analysis, rotational correlation times of triphenylbismuth molecules in the solutions and relative translational diffusion coefficient between the solvent and solute molecules have been determined. Moreover, the role of the intramolecular ¹H-¹H relaxation contribution has been revealed, depending on the motional parameters, as a result of decomposing the overall relaxation dispersion profile into contributions associated with the ¹H-¹H and ¹H-²H relaxation pathways. The possibility of accessing the contribution of the relaxation of the intrinsic protons is important from the perspective of exploiting Quadrupole Relaxation Enhancement effects as possible contrast mechanisms for Magnetic Resonance Imaging.     

Effect of dipole structures on field emission of wide-gap semiconductor emitters

It is shown that dipole structures placed in a thin (less than 1 nm) near-surface layer of a high-resistivity field emitter produce small domains on the emitting surface in which the electric field may exceed 10⁸ V/cm. In these domains, the emitter surface potential is positive, providing effective electron transport from inside the emitter to the emission boundary. Optimal dipole orientations ensuring maximal electric fields at the surface are found. When the surface density of dipoles localized in the near-surface layer is on the order of 10⁶ cm⁻², one can expect an emitter-averaged emission current density of higher than 1 A/cm². The dipole structures in the near-surface layer may persist owing to incorporated impurity molecules having a dipole moment or result from a random combination of positively charged ionized impurities and electrons captured by deep traps. Trap charging/discharging asymmetry accounts for the hysteresis of the emission I–V characteristics.     

T=1, spin-dipole strength in40Ca

Spin-dipole strength in⁴⁰Ca has been studied by inelastic scattering of 500-MeV protons and the dipole response in⁴⁰Ca is compared with the spin-dipole data from the⁴⁰Ca(p, n) reaction and nonspin-dipole data from photonuclear studies.     

The electric dipole moment of the neutron in the Kobayashi-Maskawa model

A possible mechanism for producing a neutron electric dipole moment to order G_F² in the Kobayashi-Maskawa model is proposed; the consequent order of magnitude of the dipole moment would be 10^?30 cm in units of the electric charge.     

C-REDOR curves of extended spin systems

The convergence of simulated C-REDOR curves of (infinitely) large spin systems is investigated with respect to the number of spins considered in the calculations. Taking a sufficiently large number of spins (>20,000 spins) into account enables the simulation of converged C-REDOR curves over the entire time period and not only the initial regime. The calculations are based on an existing approximation within first order average Hamiltonian theory (AHT), which assumes the absence of homonuclear dipole–dipole interactions. The C-REDOR experiment generates an average Hamiltonian close to the idealized AHT behavior even for multiple spin systems including multiple homonuclear dipole–dipole interactions which is shown from numerically exact calculations of the spin dynamics. Experimentally it is shown that calculations accurately predict the full, experimental C-REDOR curves of the multi-spin systems ³¹P–¹⁹F in apatite, ³¹P–¹H in potassium trimetaphosphimate and ¹H–³¹P in potassium dihydrogen phosphate. We also present ¹³C–¹H and ¹⁵N–¹H data for the organic compounds glycine, l-alanine and l-histidine hydrochloride monohydrate which require consideration of molecular motion. Furthermore, we investigated the current limits of the method from systematic errors and we suggest a simple way to calculate errors for homogeneous and heterogeneous samples from experimental data.     

Dipole and quadrupole cascades in the yrast region of 143Gd

The high spin states of ¹⁴³Gd have been studied via the ¹¹¹Cd(³⁵Cl,1p2n) reaction at 170 MeV. One dipole cascade has been newly found and two dipole cascades have been extended to higher spin states. A relatively long E2 cascade consisting of irregular transition energies has been found, which has only weak connections to the other dipole and quadrupole cascades. This resembles the ones recently found in ^142,143,144Eu and ¹⁴⁴Gd. The dipole and quadrupole cascades have been found to appear by turns in an energy increment of about 0.2 MeV above the yrast line. Received: 1 November 1997