IR Spectra and dipole moment function of the H2S molecule in the gas and liquid phases

The IR spectra of H₂S molecules in the gas and liquid phases and in solutions of liquefied noble gases are experimentally studied over a wide range of frequencies, including the regions of second- and third-order transitions. Based on experimental data on the parameters of the effective dipole moment, the first, second, and third derivatives of the dipole moment of the H₂S molecule with respect to the normal coordinates are recovered. The values of the first derivatives with respect to the coordinates associated with the stretching vibration are abnormally small in comparison with the higher-order derivatives. The change in the dipole moment of the molecule H₂S under the influence of the intermolecular forces on gas-liquid transition is examined. The observed anomalously large (more than 200-fold) increase in the absolute intensity of the fundamental stretching vibration band ν_str cannot be accounted for by abnormally strong intermolecular interaction forces. The increase in the absolute intensity of the ν_str band is associated with abnormally small first derivatives of the dipole moment of the gas-phase molecule. The effect of the intermolecular forces on the dipole moment is compared to that for the H₂O molecule.     

H2O分子在不同电荷态的重离子作用下的离化

利用含时密度泛函理论和局域密度近似方法，计算了H2O分子在速度为12．5α0／fs的重离子C^＋和C^2＋作用下产生的各种电荷态的H2O分子离子的几率、平均逃逸电子数和偶极矩的变化随时间的演化。计算结果表明，在重离子势最大时，电偶极矩的变化最大，重离子的电荷态越高，得到高电荷态H2O分子的几率越大；重离子远离分子时，电偶极矩的变化趋于平缓。The time-dependent density functional theory （TDDFT） and local density approximation （LDA） are used to calculate the dipole moment changes, the ionization probabilities of the H20 molecule and the time-dependent probabilities of escaped electrons in the process of excitation of H2O molecule by C^＋ , C^2＋ with energy of 2.3 MeV/u. It is shown that the dipole moment changes of H2O are the greatest and the higher the charge staate of heavy ion, the bigger the probabilities of the high charge state of H2O molecule at maximal heavy ion potential. The dipole moment changes slightly when heavy ion leaved far from molecule.     

Dynamics of orientation of adsorbed polar molecules in static electric and laser field

The rotational states of adsorbed polar molecule in the presence of static electric and laser field are investigated. In this study, we have taken two types of polar molecules, namely, one with large dipole moment and moderate rotational constant (LiCl), and the other with moderate dipole moment and large rotational constant (HBr). The adsorbed molecule is considered as rigid rotor in finite conical potential well. The eigenvalues are calculated by numerically solving the Schrödinger equation. We have shown that various properties of rotational states of the molecules are significantly influenced by the static electric field, laser field, conical potential well height and the hindrance angle. Also the use of two different polar molecules for the investigation is justified by the variation in various properties due to change in molecule.     

Effective dipole moment of rotational transitions of X 2 Y molecules

Contributions determining the rotational dependence of the effective dipole moment of molecules are calculated for the ground state of H₂S and H₂O molecules. The calculation is carried out in various ordering algorithms of perturbation theory. It is shown that the convergence of the effective dipole moment for the ground state of an H₂O molecule in the polynomial representation is rather slow in the rotational operator J _z (the convergence radius is K*≤17). Nonpolynomial forms of the dipole moment as a function of rotational operators are discussed.     

用杂化CIS-DFT方法研究外电场对乙烯激发态的影响

采用杂化CIS-DFT方法研究了外电场对乙烯分子基态和激发态性质的影响，结果表明外电场对分子几何结构，总能量，偶极矩，极化率，振子强度和激发能有显著影响。CIS-DFT的优点在于它能确定外场下分子的对称性并且给出正确的激发顺序以及分子轨道的电子组态，由此导出乙烯分子的激发态，计算结果与实验一致。首次研究了乙烯分子的外电场效应。与其他从头算方法相比，杂化CIS-DFT方法计算精度和效率相对较高，可用于研究大分子体系。     

The Orientation of the Phosphorescence Dipole Moment of Erythrosine B Within Its Molecular Frame

For an unequivocal interpretation of time-resolved phosphorescence depolarization measurements on dye molecules in biophysical systems, the orientation of the transition dipole moments within the frame of the dye has to be known. The goal of this work is to find the orientation of the phosphorescence dipole moment of erythrosine B within its molecular frame. To this end, we first determine four difference angles, exciting a molecule in two of its absorption bands and measuring the fluorescence and phosphorescence anisotropy for each excitation wavelength. The next step is to position the transition dipole moments within the molecular frame, combining the results of angle-resolved fluorescence depolarization measurements with the measured difference angles. It is shown that the phosphorescence dipole moment is tilted out of the plane of the molecule. Additionally, we find that the phosphorescence dipole moment is located above the fluorescence dipole moment and not above the absorption dipole moment. This induces an extra difference angle between the absorption and the phosphorescence dipole moments which in the past has been interpreted erroneously as a larger tilt out of the plane of the molecule.     

The sticking probability,dipole moment,and absolute coverage of CO on Ni(111)

The change in work function of a Ni(111) surface resulting from the adsorption of CO is measured continuously. Work function change is related to absolute coverage through thermal desorption measurements and LEED patterns. From the coverage-time curve, the sticking probability is determined, with an initial sticking probability of 0.91. From the relation between work function change and coverage, the dipole moment of an adsorbed CO molecule is determined to be 0.28 Debye with a negative end of the molecule projecting outward from the surface.     

Rotational Diffusion and Solvatochromic Correlation of Coumarin 6 Laser Dye

Rotational diffusion of coumarin 6 (C6) laser dye has been examined in n-decane and methanol as a function of temperature. The rotational reorientation of this probe has been measured in these solvents. It is observed that the decrease in viscosity of the solution is responsible for the decrease in the rotational relaxation time of the probe molecule. The molecule C6 has long reorientation times in n-decane solvent as compared to methanol over all temperatures. It is found that the coumarin 6 rotates slower in n-decane than in methanol especially at higher values of viscosity over temperature. Two methods are chosen to determine the ground state and excited state dipole moments. The change in dipole moments is estimated from Bakhshiev-Chamma-Viallet equations and, the ground and excited state dipole moments from Kawski et al. equations, by using the variations of the Stokes shifts with the dielectric constant and refractive index of the solvent. Our results are quite reliable which are solvatochromic correlation obtained using solvent polarity functions. The reported results show that excited state dipole moment is greater than ground state dipole moment, which indicates that the excited state is more polar than the ground state.     

On the question of determining molecular electric dipole moments from field-free frequency data

The effective masses in the Hamiltonian of a diatomic molecule with corrections for the breakdown of the Born-Oppenheimer approximation depend on the charge distribution in the molecule, and so the field-free energy levels are possible sources of information on the electric dipole moment of the molecule and other electromagnetic quantities. However, examination of explicit energy formulas and of a general indeterminacy in the effective Hamiltonian shows that this information is inseparable from effects due to the adiabatic correction to the potential. Electric dipole moments and other electromagnetic quantities obtained in this way are therefore not reliable.     

Simultaneous Determination of Force Constants and Dipole Moment Derivatives of Methane

The expressions of the effective Hamiltonian and dipole moment spectroscopic parameters in the tetrahedral formalism are used simultaneously to fit the force field and dipole moment derivatives of the methane molecule. Data, the so-called “observed parameters,” are the values of the spectroscopic parameters determined from the frequencies and line strengths analyses. The ambiguities of most parameters (in the polyad scheme) are treated consistently with the Hamiltonian reduction chosen in the frequency analyses. As an illustration, the method is applied to the tetrahedralXY₄isotopic species only. The quadratic and cubic force field constants have been determined in addition to the linear and six of the seven quadratic dipole moment derivatives. The observed parameters are reproduced with a standard deviation of 4%. The results are compared with previous works and it is moreover shown that the introduction of the dipole moment data removes some correlations between the force constants.     

Time-reversal-violating generation of static magnetic and electric fields and a problem of electric dipole moment measurement

It is shown that in the experiments for the search of the electric dipole moment of an electron (atom, molecule) the T-odd magnetic moment induced by an electric field and the T-odd electric dipole moment induced by a magnetic field will be also measured. How to distinguish these contributions is discussed here.     

Adsorption structure and work function of dicarboxylic acid on Cu(1 1 0) surface

We investigated the relation between work function and the adsorption structure of dicarboxylic acids (organic molecules) such as succinic acid (HOOC-CH₂-CH₂-COOH) and an adipic acid (HOOC-(CH₂)₄-COOH) on a Cu(1 1 0) surface (electrode) as a function of the surface temperature using a Kelvin probe (KP). The work function changes of the two acids are similar. The work function increases by adsorption at room temperature due to ionization of molecules and then decreases with increasing temperature until 450 K due to the effects of change in the dipole moment of the conformational change of the molecule. From 450 to 600 K, the work function is constant because of competition between desorption and change in the dipole moment of molecules. It then reached the clean-surface value. Experiments clarified that the work function was affected by the adsorbed difference in conformation of molecules.     

用杂化CIS-DFT方法研究外电场对乙烯激发态的影响

采用杂化CIS-DFT方法研究了外电场对乙烯分子基态和激发态性质的影响,结果表明外电场对分子几何结构,总能量,偶极矩,极化率,振子强度和激发能有显著影响.CIS-DFT的优点在于能确定外场下分子的对称性,给出正确的激发顺序以及分子轨道的电子组态,由此导出乙烯分子的激发态,结果与实验一致.首次研究了乙烯分子的外电场效应.与其他从头算方法相比,杂化CIS-DFT方法计算精确和效率相对较高,可用于研究大分子体系.     

Transferability of dipole moment derivatives between isotopic molecules: Reference molecule

To compare the dipole moment changes among different isotopic derivatives, it is necessary to refer the dipole moment changes to the same displacements in each molecule. It is therefore useful to employ a reference isotopic derivative. We propose here a kind of reference molecule which can be applied in any case, whereas the previous proposals have some limitations.     

Thermochromic shifts of the fluorescence spectra of 4-N,N-dimethylaminobenzonitrile in solution

From the temperature effect on the fluorescence bands of 4-N,N-dimethylaminobenzonitrile the dipole moments of the two emitting species are estimated as 5 (normal fluorescence) and 15 (anomalous fluorescence) Debye above the ground-state dipole moment. The dipole moment of the anomalous emitter does not change with solvent polarity and this emitter is therefore probably a molecular species (i.e. twisted charge-transfer state) and not a solvent-solute exciplex.     

Calculations of spontaneous emission rates of a single-impurity molecule in uniaxial host crystals

In a uniaxial host crystal the spontaneous emission rate of the dipole transition of the zero-phonon line of a single-impurity molecule depends on the angle between the transition dipole moment and the optical axis of a crystal and as well as on the ordinary and extraordinary refractive indices. The relative spontaneous emission rate (the spontaneous emission rate divided by the spontaneous emission rate in the case when the transition dipole moment is parallel to the optical axis) is determined through a simple formula by one coefficient. Here this coefficient is calculated as a function of the extraordinary refractive index for 40 values of the ordinary refractive index on the interval from 1.25 to 3.20. For comparison, the effects caused by the nearness to the plane interface between cinnabar crystal (HgS) and air, as an example, are calculated.     

$${{{v}}_{2}}$$ -Dependences of the Rotational Contributions to the Effective Dipole Moment of the H2O Molecule and Their Effect on the Broadening and Shift of Lines Induced by the Pressure of Buffer Gases

Optics and Spectroscopy - The dependences of the rotational contributions to the effective dipole moment of the H2O molecule on vibrational quantum number $${{{v}}_{2}}$$ , which corresponds to the...     

Quantum theory of chiral interactions in cholesteric liquid crystals

The effective chiral interaction between molecules arising from long-range quantum interactions between fluctuating charge moments is analyzed in terms of a simple model of chiral molecules. This model is based on the approximations that (a) the dominant excited states of a molecule form a band whose width is small compared to the average energy of excitation above the ground state and (b) biaxial orientational correlation between adjacent molecules can be neglected. Previous treatments of quantum chiral interactions have been based on a multipole expansion of the effective interaction energy within second-order perturbation theory. We consider a system consisting of elongated molecules and, although we invoke the expansion in terms of coordinates transverse to the long axis of constituent molecules, we treat the longitudinal coordinate exactly. Such an approximation is plausible for molecules in real liquid crystals. The macroscopic cholesteric wave vector Q (Q=2 pi/P, where P is the pitch) is obtained via Q=h/K(2), where K2 is the Frank elastic constant for twist and h is the torque field which we calculate from the effective chiral interaction kappa(IJ)a(I)xa(J) x R(IJ), where the unit vector a(I) specifies the orientation of molecule I and R(IJ) is the displacement of molecule I relative to molecule J. We identify two distinct physical limits depending on whether one or both of the interacting molecules are excited in the virtual state. When both molecules are excited, we regain the R(-8)(IJ) dependence of kappa(IJ) on intermolecular separation found previously by Van der Meer et al. [J. Chem. Phys. 65, 3935 (1976)]. The two-molecule, unlike the one-molecule term, can be interpreted in terms of a superposition of pairwise interactions between individual atoms (or local chiral centers) on the two molecules. Contributions to kappa(IJ) when one molecule is excited in the virtual state are of order R(-7)(IJ) for helical molecules which are assumed not to have a global dipole moment, but whose atoms possess a dipole moment. It is shown that for a helical molecule Q can have either the same or the opposite sign as the chiral pitch of an individual molecule, depending on the details of the anisotropy of the atomic polarizability. The one-molecule mechanism can become important when the local atomic dipoles become sizable, although biaxial correlations (ignored here) should then be taken into account. Our results suggest how the architecture of molecular dipole moments might be adjusted to significantly influence the macroscopic pitch.     

Magnetic moment oscillation in ammonium perchlorate in a DC SQUID-based magnetic resonance experiment

In this work we describe experimental results in which a DC SQUID (superconducting quantum interference device) is used as free induction decay detector. Measurements of a solid ammonium perchlorate (NH₄ClO₄) sample were performed, in zero field, at 4.2 K. Unexpected magnetic moment oscillations were detected at 1.5 kHz. The computation of the magnetic fields suggests that the proton nuclear magnetic resonance may explain the measured resonance, considering reorientation of the ammonium group by quantum tunneling of protons and a magnetic proton dipole–dipole intermolecular interaction model.