Charge distribution, dipole moment and molecular structure of silyl compounds

The formal charge distribution and hence the electric moments of a number of halosilanes and their methyl derivatives have been calculated by the method of Image and Image . The difference between the observed and the calculated values in simple halosilanes is attributed to a change in the hybridization of the terminal halogen atom and in methyl halosilanes to the enhanced electron release of the methyl group towards silicon compared with carbon.

Generation of attosecond pulses in a system with permanent dipole moment

The generation of attosecond pulses in a two-level system with permanent dipole moment is investigated. It is shown due to the presence of permanent dipole moments, that the plateau of the high-order harmonic generation spectrum can be extended to X-ray range. Moreover, attosecond pulses with higher intensity can be synthesized by using both even and odd harmonics because of their quantum interference. (c) 2006 Elsevier B.V. All rights reserved.

Quantum-confined Stark effect and built-in dipole moment in self-assembled InAs/GaAs quantum dots

Quantum-confined Stark effect and built-in dipole moment in self-assembled InAs/GaAs quantum dots (QDs), which are grown at relative low temperature (460degreesC) and embedded in GaAs p-i-n structure, have been studied by dc-biased electroreflectance. Franz-Keldysh oscillations from the undoped GaAs layer are used to determine the electric field under various bias voltages. Stark shift of -34 meV for the ground-state interband transition of the QDs is observed when the electric field increases from 105 to 308 kV/cm. The separation of the electron and hole states in the growth direction of 0.4 nm, corresponding to the built-in dipole moment of 6.4x10(-29) C m, is determined. It is found that the electron state lies above that of the hole, which is the same as that predicted by theoretical calculations for ideal pyramidal InAs QDs. (C) 2004 American Institute of Physics.

Effects of the transition dipole moment function on the dynamics of ozone photodissociation: an exact 3D quantum mechanical study

The effects of the transition dipole moment function (TDMF) on the dynamics Of O-3 photodissociation in the Hartley band have been exploited by means of exact 3D time-dependent wavepacket method using the SW potential energy surface [J. Chem. Phys. 78 (1983) 7191]. The calculations show that the explicit inclusion of the TDMF results in slight uniform reductions for the intensities of recurrence peaks of the autocorrelation function and a slight broadening of the absorption spectrum, in comparison with the result where the TDMF is assumed to be constant. The pattern of recurrence structures of the autocorrelation function is essentially unaffected. (C) 2001 Elsevier Science B.V. All rights reserved.

Study of the molecular configuration and the dipole moment in fluorinated liquid crystals

We have investigated the relationship between the molecular configuration and dipole moment of some fluorinated liquid crystals (LCs). The aeornetries of the molecules were preliminarily optimized at empirical AM1 and then were further optimized at B3LYP/6-31G(d) level. The dipole moment has been calculated. It is strongly influenced by the position and number of fluorine substituents in the benzene ring of the molecule. The polarizability, mean polarizabilities, and anisotropic polarizability of the phenylbicyclohexane (PBC) fluorine substituents are also given and discussed. (c) 2004 Wiley Periodicals, Inc.

Force constants and dipole‐moment derivatives of molecules from perturbed Hartree–Fock calculations

General expressions for the force constants and dipole‐moment derivatives of molecules are derived, and the problems arising in their practical application are reviewed. Great emphasis is placed on the use of the Hartree–Fock function as an approximate wavefunction, and a number of its properties are discussed and re‐emphasised. The main content of this paper is the development of a perturbed Hartree–Fock theory that makes possible the direct calculation of force constants and dipole‐moment derivatives from SCF–MO wavefunctions. Essentially the theory yields ∂ϕi / ∂RJα, the derivative of an MO with respect to a nuclear coordinate.

Force constants and dipole moment derivatives of molecules from perturbed Hartree-Fock calculations II. Applications to limited basis set SCF-MO wavefunctions

The perturbed Hartree–Fock theory developed in the preceding paper is applied to LiH, BH, and HF, using limited basis‐set SCF–MO wavefunctions derived by previous workers. The calculated values for the force constant ke and the dipole‐moment derivative μ(1) are (experimental values in parentheses): LiH, ke  =  1.618(1.026)mdyn/Å,μ(1)  =  −18.77(−2.0±0.3)D/ÅBH,ke  =  5.199(3.032)mdyn/Å,μ(1)  =  −1.03(−)D/Å;HF,ke  =  12.90(9.651)mdyn/Å,μ(1)  =  −2.15(+1.50)D/Å. The values of the force on the proton were calculated exactly and according to the Hellmann–Feynman theorem in each case, and the discrepancies show that none of the wavefunctions used are close to the Hartree–Fock limit, so that the large errors in ke and μ(1) are not surprising. However no difficulties arose in the perturbed Hartree–Fock calculation, so that the application of the theory to more accurate wavefunctions appears quite feasible.

Electron and neutron electric dipole moment in the 3-3-1 model with heavy leptons

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The search for the neutron electric dipole moment

A permanent electric dipole moment of the neutron violates time reversal as well as parity symmetry. Thus it also violates the combination of charge conjugation and parity symmetry if the combination of all three symmetries is a symmetry of nature. The violation of these symmetries could help to explain the observed baryon content of the Universe. The prediction of the Standard Model of particle physics for the neutron electric dipole moment is only about 10e−32 ecm. At the same time the combined violation of charge conjugation and parity symmetry in the Standard Model is insufficient to explain the observed baryon asymmetry of the Universe. Several extensions to the Standard Model can explain the observed baryon asymmetry and also predict values for the neutron electric dipole moment just below the current best experimental limit of d n < 2.9e−26 ecm, (90% C.L.) that has been obtained by the Sussex-RAL-ILL collaboration in 2006. The very same experiment that set the current best limit on the electric dipole moment has been upgraded and moved to the Paul Scherrer Institute. Now an international collaboration is aiming at increasing the sensitivity for an electric dipole moment by more than an order of magnitude. This thesis took place in the frame of this experiment and went along with the commissioning of the experiment until first data taking. After a short layout of the theoretical background in chapter 1, the experiment with all subsystems and their performance are described in detail in chapter 2. To reach the goal sensitivity the control of systematic errors is as important as an increase in statistical sensitivity. Known systematic efects are described and evaluated in chapter 3. During about ten days in 2012, a first set of data was measured with the experiment at the Paul Scherrer Institute. An analysis of this data is presented in chapter 4, together with general tools developed for future analysis eforts. The result for the upper limit of an electric dipole moment of the neutron is |dn| ≤ 6.4e−25 ecm (95%C.L.). Chapter 5 presents investigations for a next generation experiment, to build electrodes made partly from insulating material. Among other advantages, such electrodes would reduce magnetic noise, generated by the thermal movement of charge carriers. The last Chapter summarizes this work and gives an outlook.

New search for the Neutron Electric Dipole Moment using ultracold neutrons at the Spallation Neutron Source

This document introduces the planned new search for the neutron Electric Dipole Moment at the Spallation Neutron Source at the Oak Ridge National Laboratory. A spin precession measurement is to be carried out using Ultracold neutrons diluted in a superfluid Helium bath at T = 0.5 K, where spin polarized 3He atoms act as detector of the neutron spin polarization. This manuscript describes some of the key aspects of the planned experiment with the contributions from Caltech to the development of the project.

Techniques used in the design of magnet coils for Nuclear Magnetic Resonance were adapted to the geometry of the experiment. Described is an initial design approach using a pair of coils tuned to shield outer conductive elements from resistive heat loads, while inducing an oscillating field in the measurement volume. A small prototype was constructed to test the model of the field at room temperature.

A large scale test of the high voltage system was carried out in a collaborative effort at the Los Alamos National Laboratory. The application and amplification of high voltage to polished steel electrodes immersed in a superfluid Helium bath was studied, as well as the electrical breakdown properties of the electrodes at low temperatures. A suite of Monte Carlo simulation software tools to model the interaction of neutrons, 3He atoms, and their spins with the experimental magnetic and electric fields was developed and implemented to further the study of expected systematic effects of the measurement, with particular focus on the false Electric Dipole Moment induced by a Geometric Phase akin to Berry’s phase.

An analysis framework was developed and implemented using unbinned likelihood to fit the time modulated signal expected from the measurement data. A collaborative Monte Carlo data set was used to test the analysis methods.

The dipole moments and molecular structure of substituted acetamides

Thioacetamide has a dipole moment substantially higher than the vector sum of the normal characteristic moments of its constituent bonds. However, the effect can reasonably be accounted for on the scheme of alterations in charge distribution and hence of bond moments proposed by Smith, Ree, Magee and Eyring. The same is probably true for chloroacetamide even though the problem of rotation about the C-C single bond renders the conclusion less certain. For cyanoacetamide, the observed moment cannot be accounted for satisfactorily on this basis.

The dipole moments and molecular structure of chloral and bromal hydrates

The dipole moment of chloral hydrate is 2·07 D and 2·65 D at 35° in benzene and dioxane solutions respectively. Bromal hydrate has a moment of 2·56 D in benzene solution. The moments observed can reasonably be accounted for on the scheme of Smith et al. and the results have been discussed in terms of the possible structures of these molecules.

Dipole moments and molecular structure of picrates of aromatic hydrocarbons and heterocyclic amines

Dipole moment measurements have been made in the case of a few aromatic hydrocarbon picrates, the values obtained being 2·18, 2·25, 2·97 (all in Debye units) for picrates of naphthalene, acenaphthene and phenanthrene respectively and the results discussed in terms of Mulliken's theory. Measurements have also been extended to include a few salt-like heterocyclic amine picrates.

Determination of the vibrational transition moment ratio for the Coriolis interacting v9 and v10 fundamentals of allene

Comparison between observed and calculated infrared band contours has been made to determine the vibrational transition moment ratio |M10/M9| for the Coriolis interacting ν9 and ν10 perpendicular fundamentals of allene-h4. The ratio obtained is appreciably lower than that of a previous estimate and the result obtained by integrated band intensity measurements of Overend and Crawford. From the best estimate of the ratio, the dipole moment derivatives of the two bands are determined; the value for the weaker band ν9 is subject to a large uncertainty.

Calculations of rovibrational energies and dipole transition intensities for polyatomic molecules using MULTIMODE

We report rigorous calculations of rovibrational energies and dipole transition intensities for three molecules using a new version of the code MULTIMODE. The key features of this code which permit, for the first time, such calculations for moderately sized but otherwise general polyatomic molecules are briefly described. Calculations for the triatomic molecule BF(2) are done to validate the code. New calculations for H(2)CO and H(2)CS are reported; these make use of semiempirical potentials but ab initio dipole moment surfaces. The new dipole surface for H(2)CO is a full-dimensional fit to the dipole moment obtained with the coupled-cluster with single and double excitations and a perturbative treatment of triple excitations method with the augmented correlation consistent triple zeta basis set. Detailed comparisons are made with experimental results from a fit to relative data for H(2)CS and absolute intensities from the HITRAN database for H(2)CO.