Blackbody radiation shift of the Al<Superscript>+</Superscript> clock transition

The blackbody radiation shift of the Al⁺ 3s^{2 1}S^e ₀ ↦ 3s3p ³P^○ ₀ clock transition is evaluated. The polarizabilities of the two states are determined by means of configuration interaction calculations in conjunction with oscillator strength sum rules. The ground state polarizability was 24.14 ±0.12 a.u. while the metastable state polarizability was 24.62 ±0.25 a.u. The derived frequency shift at 300 K was Δν= -0.0042 ±0.0032 Hz. Some auxiliary sum rules are evaluated that allow for the conversion of a finite frequency polarizability difference to a static polarizability difference.     

Direct measurement of the nuclear magnetic dipole moment of Ho165 with the atomic beam magnetic resonance method

With an atomic beam magnetic resonance apparatus four rf transitions between different Zeeman levels of the⁴ I _15/2 ground state of Ho¹⁶⁵ have been measured in an external magnetic field of about 3000 Gauss. The interaction between the nuclear magnetic dipole moment and the external field could be deduced from these measurements. Because the magnetic field was measured by calibration transitions in K³⁹, Rb⁸⁵ and Rb⁸⁷, the following value could be determined for the nuclear magnetic dipole moment: μ _I (Ho¹⁶⁵)=4.094(44) μ _n (uncorrected for diamagnetic shielding). Thegj-factor of the ground state of Ho¹⁶⁵ was measured to begj(⁴ I _15/2, Ho¹⁶⁵)=1.1951445(40).     

Variation of potential energy surface height and bound state depth induced by laser phase along the reaction path in atom-molecule reactions: Application to Li + CH<Subscript>4</Subscript> → LiH + CH<Subscript>3</Subscript>

Laser atom-molecule reaction interaction through polarizability and dipole moment contribution leads to potential energy surface barrier reshaping and bound states along the reaction path. The polarizability is maximum in the transition state. We will show here by using gauge representation (electric field gauge) for wave length λ = 20.6 μm, intensity I = 1 × 10¹² W/cm², I = 5 × 10¹² W/cm², I = 1 × 10¹³ W/cm², I = 3 × 10¹³ W/cm², that we can create laser induced potential energy surface barrier reshaping in the transition state region (–1–0.5 a. u.). We illustrate such effects for the LiH + CH₃ ? Li + CH₄ reaction with a barrier using ab-initio methods for calculating the reaction path, polarizability and dipole moment contribution of the atom-molecule reaction.     

Optical properties and upconversion in Yb3+—Tm3+ co-doped oxyfluoride glasses and glass ceramics

A theoretical study has explored the changes brought upon the electron density of the open (C_2v) and cyclic (D_3h) forms of ozone by protonation. Although protonation results in a strong deformation of the electron density of ozone with notably different charge distributions for the stable forms of O₃H⁺, the electric dipole polarizability is almost stable for the open protonated species. The polarizability of the cyclic form is less affected by protonation than that of the open one. The anisotropy of the dipole polarizability discriminates very clearly between open and closed protonated ozone. We expect the present findings to advance our understanding of the chemical reactivity of O₃H⁺.     

Hyperfine structure measurements in metastable states of165Ho

The hyperfine structure constants and the electronic g _J factor of the state 4f ¹¹ 6s ^{2 4} I _11/2 belonging to the holmium ground multiplet have been measured using the atomic beam magnetic resonance technique combined with a state-selective laser-induced detection of the resonant atoms. By the same method the g _J factor of the level 4f ¹¹6s ²⁴ I _9/2 was determined, while the hyperfine structures of this metastable state and of two high-lying even parity states have been investigated by high resolution laser spectroscopy. The results for the experimentalA andB factors of all four members of the ground multiplet allow a least-squares evaluation of the three magnetic dipole and the three electric quadrupole effective radial parameters for the configuration 4f ¹¹ 6s ² of holmium, yielding an accurate value for the spectroscopic nuclear electric quadrupole moment:Q _hfs(¹⁶⁵Ho)=2.716(9)b (uncorrected for quadrupole shielding). From a comparison to the quadrupole moments measured in mesic holmium atoms the shielding factor could be estimated.     

Electrooptical Absorption Measurements (EOAM) Testify Existence of two Conformers of Prodan and Laurdan with Different Dipole Moments in Equilibrium Ground and Franck-Condon Excited State

The results from the electrooptical absorption measurements (EOAM) on the equilibrium ground and excited Franck-Condon state dipole moments of Prodan and Laurdan in 1,4-dioxane are presented. As follows from experiments Prodan and Laurdan in the equilibrium ground and excited Franck-Condon state have two conformers with considerably different dipole moments. The electrical dipole moments and the transition dipole moment, obtained from the short-wavelength region of the absorption spectrum are parallel. The electrical dipole moments measured at the long-wavelength spectral region are parallel to each other but not parallel to the transition dipole moment m _a. The angle θ between the transition dipole moment m _a and the dipole moment in the equilibrium ground state μ _g of the long-wavelength conformer is about 30⁰ for both probes. Obtained results evidence that donor-acceptor pairs of the short-wavelength and long-wavelength conformers are not located on the same axis. Two low-energy conformers of Prodan have been found by density functional theory (DFT) calculations, differing in the orientation of the carbonyl group towards the naphthalene system.     

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.     

High-resolution measurements of the 1 ← 0 infrared absorption band of hydrogen iodide

The ν₁ fundamental band of FNO has been studied by the technique of CO laser Stark spectroscopy. The band origin was determined to be 1844.099 cm^?1, and values for the rotational and centrifugal distortion constants of the (100) excited vibrational state were found. The ground state dipole moment components were determined to be μ_a = 1.690 and μ_b = 0.370 D, for a total dipole moment of 1.730 D, and a relatively large reduction (5%) was found in μ for the (100) state relative to the ground state.     

Static electric dipole polarizability of lithium atoms in Debye plasmas

<正>The static electric dipole polarizabilities of the ground state and n≤3 excited states of a lithium atom embedded in a weekly coupled plasma environment are investigated as a function of the plasma screening radium.The plasma screening of the Coulomb interaction is described by the Debye-H（u|¨）ckel potential and the interaction between the valence electron and the atomic core is described by a model potential.The electron energies and wave functions for both the bound and continuum states are calculated by solving the Schrodinger equation numerically using the symplectic integrator.The oscillator strengths,partial-wave,and total static dipole polarizabilities of the ground state and n≤3 excited states of the lithium atom are calculated.Comparison of present results with those of other authors, when available,is made.The results for the 2s ground state demonstrated that the oscillator strengths and the static dipole polarizabilities from np orbitals do not always increase or decrease with the plasma screening effect increasing, unlike that for hydrogen-like ions,especially for 2s→3p transition there is a zero value for both the oscillator strength and the static dipole polarizability for screening length D = 10.3106a₀,which is associated with the Cooper minima.     

One-electron spectrum of Lu2+: Relativistic energies,transition probabilities and dipole polarizability

Calculations are reported of relativistic model-potential ionization energies and transition probabilities in the one-electron spectrum of doubly ionized lutetium. The approach employed includes both valence-core electron exchange and correlation. The influence of polarization of the core by the valence electron on ionization energies and transition probabilities has been studied. Strong cancellation effects, similar to those found previously for the Yb(II) spectrum, have been found for higher transitions of the principal series. Energies are predicted for some states that have not yet been determined experimentally. Computed oscillator strengths for the principal series are employed to obtain a tentative value for the static dipole polarizability of the doubly-ionized lutetium ground state … 4f¹⁴6s²S_{$\text{1}\text{2}$}.     

CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

Solvatochromic Effect on the Photophysical Properties of Two Coumarins

The absorption and emission spectra of two coumarins namely 7, 8 benzo-4-azidomethyl coumarin (C₁) and 6-methoxy-4-azidomethyl coumarin (C₂) have been recorded at room temperature in solvents of different polarities. The ground state dipole moments (μ _g ) of two coumarins were determined experimentally by Guggenheim method. The exited state (μ _e ) dipole moments were estimated from Lippert’s, Bakhshievs and Chamma-Viallet’s equations by using the variation of Stoke’s shift with the solvent dielectric constant and refractive index. The ground and excited state dipole moments were calculated by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was observed that dipole moments of excited state were higher than those of the ground state, indicating a substantial redistribution of the π-electron densities in a more polar excited state for two coumarins.     

Solvent Effect on Absorption and Fluorescence Spectra of Three Biologically Active Carboxamides (C<Subscript>1</Subscript>, C<Subscript>2</Subscript> and C<Subscript>3</Subscript>). Estimation of Ground and Excited State Dipole Moment from Solvatochromic Method Using Solvent Polarity Parameters

The absorption and fluorescence spectra of three Carboxamides namely (E)-2-(4-Chlorobenzylideneamino)-N-(2-chlorophenyl)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₁), (E)-N-(3-Chlorophenyl)-2-(3, 4-dimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₂) and (E)-N-(3-Chlorophenyl)-2-(3, 4, 5-trimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₃) have been recorded at room temperature in solvents of different polarities using dielectric constant (ε) and refractive index (n). Experimental ground (μ_g) and excited (μ_e) state dipole moments are estimated by means of solvatochromic shift method and also the excited dipole moments are estimated in combination with ground state dipole moments. It was estimated that dipole moments of the excited state were higher than those of the ground state of all three molecules. Further, the changes in dipole moment (Dm \Delta \mu ) were calculated both from solvatochromic shift method and on the basis of microscopic empirical solvent polarity parameter (E_T^N E_T^N ) and the values are compared.     

Theoretical study of molecular properties of low-lying electronic excited states of H2O and H2S

Geometries, excitation energies, dipole moments and dipole polarisability tensor components of the ground and four lowest excited states ³ B ₁, ¹ B ₁, ³ A ₂, ¹ A ₂ of the H₂O and H₂S molecules were calculated at the CASSCF, CASPT2, CCSD and CCSD(T) level of approximation. Vertical excitation and equilibrium transition energies of these states, having the Rydberg character, are reported too. Properties of both molecules in the ground and in low lying excited states are compared and discussed from the point of view of their molecular electronic structure. Upon excitation we observe dramatic changes of dipole moments and polarisabilities with respect to the ground state. We stress the change of the polarity of H₂O in all excited states accompanied by the enhancement of the dipole polarisability by an order of magnitude. Large, even if less pronounced, are changes of electric properties of H₂S in its excited states. Dipole moments and dipole polarisabilities of ³ B ₁, ¹ B ₁ states of H₂S and H₂O behave quite analogously in comparison to their respective ground state. The general pattern of properties for both molecules in their ³ A ₂ and ¹ A ₂ excited states is more different due to a pronounced participation of the sulphur d-orbitals in these states of the H₂S molecule.     

Calculation of Structures and Deexcitation Process of H2Mu+ Molecules

Energy levels, interparticle distances and dipole transition rates of H₂Mu⁺ molecules were calculated with the coupled rearrangement channel method. The structure of the ground state of H₂Mu⁺ is an isosceles triangle, while that of H₃ ⁺ is an equilateral triangle. The calculated dipole transition rates are small compared with the muon decay rate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electric dipole moments and nuclear hyperfine interactions for H2S,HDS, and D2S

Electric dipole moments and nuclear hyperfine coupling constants for several low-energy rotational states of the ground vibrational state of H₂S, HDS, and D₂S have been determined by molecular beam electric resonance spectroscopy. Analysis of the Stark effects for radiofrequency spectra of the lowest rotational levels gives dipole moments of 0.978325 (10) D for H₂S (J = 1, τ = 0), 0.977294 (20) D for D₂S (J = 1, τ = 0), and 0.977484 (60) D for HDS (J = 1, τ = 1 and J = 2, τ = 0). The electric field gradient tensor at the deuterium nucleus, the nuclear spin-spin tensor, and the spin-rotation tensor were evaluated from the hyperfine components of the radiofrequency spectra. The accuracy of these tensors was moderately improved over earlier measurements. From the H₂S spin-rotation tensor, the average paramagnetic shielding for the protons was found to be σ_av^p = ?104.84 (40) ppm. Combining this result with the proton NMR absolute chemical shift allowed the average diamagnetic shielding to be calculated as σ_av^d = 135.7 (5) ppm.     

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.     

Microwave spectrum of the hydrogen sulfide molecule H232S in the ground state

Frequencies, line strengths, and intensities of microwave electric dipole rotational transitions of H₂³²S in the ground state have been calculated. The calculation was based on representation of the effective rotational Hamiltonian operator in the form of a Pade operator. As initial information, all known microwave data on frequencies of rotational transitions of H₂³²S in the ground state were used. Some of these data were obtained in the present paper.     

Ring currents in six-membered heterocycles: the diazaborinines (CH)2B2N2

Six of the eleven possible cyclic isomers (CH)₂B₂N₂ are found, by geometric optimization at a correlated level of theory, to have planar closed-shell ground states. Current density maps calculated with distributed-origin coupled Hartree–Fock theory wavefunctions show that all six of these have delocalized π-electron systems supporting diamagnetic ring currents. In comparison with benzene at the same level of theory, the isomer with lowest energy, 1,3,2,4 diazadiborinine, has a 5% greater centre of ring shielding, but 20–25% smaller mean magnetizability, mean polarizability and polarizability anisotropy.