Current rectification in single molecule C59N: Effect of molecular polarity induced dipole moment

By applying non-equilibrium Green's function formalism combined with density functional theory, we have investigated the electronic transport properties of nitrogen doped fullerene absorbed on the self-assembled alkanethiol monolayer. The molecular dipole moment, which in microscopy leads to the molecule-electrode coupling changing asymmetrically is responsible for the observed molecular rectification.     

Spectral line parameters in the (2 ← 0) overtone band and the dipole moment function of the HI molecule

We present here new high-resolution experimental data on the linestrengths and pressure-broadened Lorentzian widths for the P₂(13) to R₂(12) vibration-rotation lines in the first overtone absorption band of hydrogen iodide. By combining the measured linestrengths with our previous results for the fundamental band [J. Mol. Spectrosc. 218 (2003) 75] and with other published data for the higher-overtone bands of this molecule, an improved dipole moment expansion as a function of the dimensionless reduced nuclear displacement x is obtained: μ(x)=0.4471(5)−0.0772(2)x+0.542(3)x²−1.90(2)x³. This experimental dipole moment function is compared with the results of a few recent non-relativistic and relativistic ab initio calculations. The agreement between theoretical and experimental Herman-Wallis coefficients for the first two vibrational bands of HI is found best as ever reported before.     

Measurements of line intensities and determination of transition moment parameters from experimental data for the ν1 and ν3 bands of D2S

First measurements of line intensities for ν₁ and ν₃ bands of D₂³²S are reported. About 300 intensities of D₂³²S vibration–rotation lines were obtained from experimental high-resolution spectra recorded in the 1810–2051 cm⁻¹ region with the Fourier Transform Spectrometer built in Reims. Empirical values of transition moment parameters for ν₁ and ν₃ bands of D₂³²S were determined for the first time using a least-square fit to the observed intensities. Experimental D₂³²S intensities were compared with recent global variational predictions [Vl.G. Tyuterev, L. Régalia-Jarlot, D.W. Schwenke, S.A. Tashkun, Y.G. Borkov, C. R. Phys. 5 (2004) 189–199] computed from isotopically invariant potential and dipole moment functions of the hydrogen sulphide molecule. Average discrepancy between these calculations and our observed data was 0.03 cm⁻¹ for line positions of this spectral range. The discrepancy between these calculations and our measurements for the sum of line intensities was 5.5% and 3.5% for the ν₁ and ν₃ bands, correspondingly.     

Spectral line parameters in the (4 ← 0) overtone band and the dipole moment function of HI

We present new measurements of the line strengths in the third vibrational overtone band in pure HI and its mixtures with Ne, Ar, and Xe, and report results of the Herman-Wallis analysis for this band. Significance of the higher-order terms in the polynomial representation of the dipole moment function is discussed. It is concluded that the spectroscopic data yield the dipole moment function fully described by a cubic polynomial in powers of the reduced displacement from the equilibrium bond length. In the Padé approximant for the dipole moment function, the vicinity of the saddle point near equilibrium also can be accurately fitted with a cubic polynomial. Pressure line broadening and shifting parameters are reported for mixtures of HI with rare gases.     

Determination of the molecular dipole moment of bromofluoromethane: Microwave Stark spectra and ab initio calculations

The electric dipole moment of bromofluoromethane, CH₂⁷⁹BrF, has been determined with a good accuracy by observing the second order ΔM_J = 0 Stark spectrum of the J = 3_2,1 ← 3_1,2, J = 5_2,3 ← 5_1,4 and J = 5_2,4 ← 5_1,5 rotational transitions. In addition, the equilibrium geometry and dipole moment have been evaluated using highly accurate ab initio calculations. By comparing the experimental [μ_a = 0.3466(11) D and μ_b = 1.704(26) D] and theoretical [μ_a = −0.339 D and μ_b = −1.701 D] dipole moment components, a very good agreement has been found.     

Three-dimensional ab initio dipole moment surfaces and stretching vibrational band intensities of the XH3 molecules

Stretching vibrational band intensities of XH₃ (X=N, Sb) molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model.The dipole moment surfaces of NH₃ and SbH₃ are calculated with the density functional theory and at the correlated MP2 level,respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides (NH₃, PH₃,AsH₃ and SbH₃) are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit.     

Analytic solution of the wave equation for an electron in the field of a molecule with an electric dipole moment

We relax the usual diagonal constraint on the matrix representation of the eigenvalue wave equation by allowing it to be tridiagonal. This results in a larger representation space that incorporates an analytic solution for the non-central electric dipole potential cosθ/r², which was believed not to belong to the class of exactly solvable potentials. Therefore, we were able to obtain a closed form solution of the three-dimensional time-independent Schrödinger equation for a charged particle in the field of a point electric dipole that could carry a nonzero net charge. This problem models the interaction of an electron with a molecule (neutral or ionized) that has a permanent electric dipole moment. The solution is written as a series in a basis composed of special functions that support a tridiagonal matrix representation for the angular and radial components of the wave operator. Moreover, this solution is for all energies, the discrete (for bound states) as well as the continuous (for scattering states). The expansion coefficients of the radial and angular components of the wavefunction are written in terms of orthogonal polynomials satisfying three-term recursion relations. For the Coulomb-free case, where the molecule is neutral, we calculate critical values for its dipole moment below which no electron capture is allowed. These critical values are obtained not only for the ground state, where it agrees with already known results, but also for excited states as well.     

Ab initio dipole moment and theoretical rovibrational intensities in the electronic ground state of PH3

We report a six-dimensional CCSD(T)/aug-cc-pVTZ dipole moment surface for the electronic ground state of PH₃ computed ab initio on a large grid of 10 080 molecular geometries. Parameterized, analytical functions are fitted through the ab initio data, and the resulting dipole moment functions are used, together with a potential energy function determined by refining an existing ab initio surface in fittings to experimental wavenumber data, for simulating absorption spectra of the first three polyads of PH₃, i.e., (ν₂, ν₄), (ν₁, ν₃, 2ν₂, 2ν₄, ν₂ + ν₄), and (ν₁ + ν₂, ν₃ + ν₂, ν₁ + ν₄, ν₃ + ν₄, 2ν₂ + ν₄, ν₂ + 2ν₄, 3ν₂, 3ν₄). The resulting theoretical transition moments show excellent agreement with experiment. A line-by-line comparison of the simulated intensities of the ν₂/ν₄ band system with 955 experimental intensity values reported by Brown et al. [L.R. Brown, R.L. Sams, I. Kleiner, C. Cottaz, L. Sagui, J. Mol. Spectrosc. 215 (2002) 178-203] gives an average absolute percentage deviation of 8.7% (and a root-mean-square deviation of 0.94 cm⁻¹ for the transition wavenumbers). This is very remarkable since the calculations rely entirely on ab initio dipole moment surfaces and do not involve any adjustment of these surfaces to reproduce the experimental intensities. Finally, we predict the line strengths for transitions between so-called cluster levels (near-degenerate levels formed at high rotational excitation) for J up to 60.     

Relativistic correction to the dipole polarizability of a hydrogenic ion

The first relativistic correction of orderα ² to the dipole polarizability of a hydrogenic ion has been investigated by using mean excitation energy of the ion within the second-order perturbation theory. The density-dependent mean excitation energy is estimated via Bethe theory for the stopping cross section for a moving point charge interacting with the hydrogenic ion. In this approach only the unperturbed Dirac wavefunctions are required to evaluate the appropriate matrix elements. The first relativistic correction turns out to be − (13/12)(αZ)². This has the correct sign and is within 5% of the exact result which is −(28/27)(αZ)².     

On the effects on a Landau-type system for an atom with no permanent electric dipole moment due to a Coulomb-type potential

We analyse the bound states for a Landau-type system for an atom with no permanent electric dipole moment subject to a Coulomb-type potential. By comparing the energy levels for bound states of the system with the Landau quantization for an atom with no permanent electric dipole moment (Furtado et al., 2006), we show that the energy levels of the Landau-type system are modified, where the degeneracy of the energy levels is broken. Another quantum effect investigated is a dependence of the angular frequency of the system on the quantum numbers associated with the radial modes and the angular momentum. As examples, we obtain the angular frequency and the energy levels associated with the ground state and the first excited state of the system.     

Autocorrelation function formulations and the turbulence dissipation rate: Application to dispersion models

The classical statistical diffusion theory and the binomial autocorrelation function are used to obtain a new formulation for the turbulence dissipation rate ε. The approach employs the Maclaurin series expansion of a logarithm function contained in the dispersion parameter formulation. The numerical coefficient of this new relation for ε is 100% larger than the numerical coefficient of the classical relation derived from the exponential autocorrelation function. A similar approach shows that the dispersion parameter obtained from the even exponential autocorrelation function does not result in a relation for ε and, therefore, is not suitable for application in dispersion models. In addition, a statistical comparison to experimental ground-level concentration data demonstrates that this newly derived relation for ε as well as other formulations for the turbulence dissipation rate are suitable for application in Lagrangian stochastic dispersion models. Therefore, the analysis shows that there is an uncertainty regarding the turbulence dissipation rate function form and the autocorrelation function form.     

Absorption profiles of HCl for the J = 1-0 rotational transition: Foreign-gas effects measured for N2, O2, and Ar

Line profiles of the J = 1-0 transition of the hydrogen chloride, H³⁵Cl and H³⁷Cl isotopomers, were measured with a BWO-based submillimeter-wave spectrometer at AIST in real form: three hyperfine transitions for each isotopomer, i.e., total six lines at 625 and 626 GHz. The effect of foreign gases on the broadening and shift was determined for N₂, O₂, and Ar. The modified Voigt function was applied as the line shape function for preliminary analysis, where the collisional-narrowing effect was clearly observed. In the final analysis, we applied the Galatry function and determined the integral intensity, line center position, Lorentzian width, and contraction parameter for each absorption line. The magnitudes of the foreign-gas pressure-broadening coefficients decrease in order of N₂, O₂, and Ar. The line-shift coefficients were clearly observed, the magnitudes of which decrease in order of Ar, O₂, and N₂. The pressure dependence of contraction parameter was determined, although with poor precision.     

Mass-Analyzed Ion Kinetic Energy Spectra of Chloroanisols: Application to the Interpretation of the Mass Spectra of Methoxybenzenesulfonyl Chlorides

There have been many studies of the fragmentation of metastable ions in the field-free regions of sector mass spectrometers.¹ Such ions have a lower internal energy than do ions fragmenting in the source. As a result, their reactions are often more sensitive to     

Acceleration of the iterative solver in the discrete dipole approximation: Application to the orientation variation of irregularly shaped particles

We have applied a method of reducing the number of iterations required to solve a system of linear equations in the discrete dipole approximation. This method obtains an initial guess of dipole polarization from those with similar particle characteristics (e.g., the size parameter and refractive index) calculated a priori. If the initial guess is closer to the solution, the number of iterations of the linear equation solution becomes smaller than that calculated with an arbitrary initial value.

This method was applied to various particle orientations using spline interpolation of the initial guess of dipole polarization from orientations calculated a priori.

We studied three types of particle model: an aggregate, a deformed sphere with moderate surface roughness, and a particle with a large number of edges. For the particle with a large number of edges, we propose a new model called the overlapping mixture of multiple tetrahedra (OMMT).

The proposed method is most advantageous for particles with moderate surface roughness (e.g., a deformed sphere), for which the calculation time was reduced to 20–40% of the original calculation time. For OMMT and an aggregate, the computation time was reduced to 30–60% and 40–90%, respectively. The differences in the scattering coefficient, absorption coefficient, intensity and polarization introduced by our method were less than 0.008%, 0.03%, 0.1%, and 0.08%, respectively.

If the light scattering properties vary slowly with the orientation variation, interpolation of the results is more efficient than the proposed method and produces only a small difference in the results. However, the interpolation of the results fails for particles such as BCCA64, for which our proposed method produces more accurate results.     

Application of the Wigner distribution function to studying spectral changes of twisted anisotropic Gaussian Schell-Model beams

By using the Wigner distribution function (WDF), a general closed-form expression for the spectrum of twisted anisotropic Gaussian Schell-model (AGSM) beams in passage through a first-order ABCD system is derived. The spectral changes of twisted AGSM beams propagating in free space and through a thin lens, and the spectral changes of conversional Gaussian-Schell model (GSM) beams are treated as special cases of our general expression. Our theoretical and numerical results show that the WDF provides a powerful and simple tool in analyzing propagation properties of general AGSM beams. Specifically, the spectral behavior of twisted AGSM beams and conventional GSM beams can be treated in a unified and analytical way.     

Construction of a Langevin model from time series with a periodical correlation function: Application to wind speed data

A Langevin-type equation for stochastic processes with a periodical correlation function is introduced. A procedure of reconstruction of the equation from time series is proposed and verified on simulated data. The method is applied to geophysical time series–hourly time series of wind speed measured in northern Italy–constructing the macroscopic model of the phenomenon.     

“Anomalous” pseudodielectric function of GaN: Experiment, modelling and application to the study of surface properties

Studying GaN films exposed to Ar plasma by spectroscopic ellipsometry and reflectance, we found an “anomalous” pseudodielectric function (PDF) for which the imaginary part is significantly higher as compared to GaN, while the real part of the PDF remains close to the value for GaN. In addition, a higher reflectance at low angles of incidence was observed. The data are explained in terms of a thin highly absorbing surface layer arising due to non-stoichiometry in the near-surface region. Comparison to samples grown by molecular beam epitaxy shows that similar mechanisms are responsible for optical properties of the surfaces of films obtained under Ga-rich conditions.     

Tensorial development of the rovibronic Hamiltonian and dipole moment operators for XY3Z molecules with a degenerate electronic state: Preliminary application to the CH3O radical

We present a development of the Hamiltonian and transition moment operators of XY₃Z (C_3v) symmetric tops molecules in a degenerate electronic state with the aid of a tensorial formalism developed in a recent paper [A. El Hilali, V. Boudon, M. Loëte, J. Mol. Spectrosc. 239 (2006) 41-50]. Electronic operators are defined from group theory properties. They provide a new approach to build an effective rovibronic Hamiltonian as well as an effective dipole moment operator for rovibronic transition of XY₃Z molecules. This model is studied qualitatively thanks to the tensorial algebra properties. Expressions of the matrix elements are derived for these operators. A first simple application to the ground electronic state of CH₃O is proposed as an illustrative example.     

Application of the Wigner distribution function to complex-argument Hermite– and Laguerre–Gaussian beams beyond the paraxial approximation

The Wigner distribution function (WDF) is applied to study the propagation of complex-argument Hermite–Gaussian (HG) and Laguerre–Gaussian (LG) beams beyond the paraxial approximation. The analytical expressions for their intensity distributions in free-space propagation are derived, which are expressed in terms of Hermite polynomials for nonparaxial complex-argument HG beams and in terms of the sum of finite Hermite polynomials for nonparaxial complex-argument LG beams. A detailed comparison of the WDF approach, series expansion method and paraxial expressions is made, which shows that in the paraxial regime the WDF approach and series expansion method deliver consistent results with that of paraxial expressions. Beyond the paraxial approximation, the WDF approach offers convergent results, whereas the series expansion method has a limited applicable range, within which it gives consistent results with that of WDF approach but beyond which it gives unrealistic and divergent results.     

Numerical resolution of the modified Langevin equation using a differential expression: Application to the Jiles magnetostriction law of approach

The Langevin equation is classically used to model the anhysteretic magnetization curve. A modified version of this equation has been introduced by Jiles to take into account the effects of magnetostriction on the anhysteretic magnetization behavior when a ferromagnetic material undergoes mechanical stresses. The numerical resolution of the modified Langevin equation is usually performed with a root-finding algorithm. In this paper, a differential form of the modified Langevin equation is proposed, allowing a faster numerical resolution.