Polarity of the Medium and Quenching of Fluorescence of Caratenoids and Phthalimides

The relation for the dependence of the rate of radiationless energy conversion of the S ₁ state k _q on the polarity of the medium, obtained previously by the author, has been used to interpret the known literature data on the lifetime of the S ₁ state of solutions of some caratenoids and phthalimides. It has been shown that in alcohols and water (normal and deuterated ones) the fluorescence quenching of 4-amino-, 4-methylamino-, and 4-dimethylamino-N-methylphthalimides (4AMP, 4MAMP, and 4DMAMP) as well as of peridinine in alcohols is due to H-bond formation. It has been established that a twofold increase in the number of amine atoms of hydrogen on passing from 4MAMP to 4AMP, as well as deuteration of solvents in the case of 4DMAMP, is followed by a decrease in k _q by a factor of 1.6 and 1.75, respectively. The mechanism of quenching in complexes formed with solvent molecules by means of the H-bond is discussed. It has been concluded that the quenching of fluorescence of phthalimides in such complexes is mainly due to the intersystem crossing initiated by the oscillations of the protons or deuterons of the H-bonds.     

Theoretical calculation of the dipole moment function of the aΠ state of NO

The potential energy curve and theoretical dipole moment function of the a⁴Π state of NO have been determined using full-valence and first-order configuration interaction wavefunctions. Using these two different wavefunctions, the dipole moments of the a⁴Π, v = 3 level have been found equal, respectively, to 0.16 D and 0.30 D, with the polarity N⁺O⁻. These values compare well with the value of |0.20 ± 0.04| D determined by Lisy and Klemperer. The first derivative of the dipole moment has also been calculated to be equal to 1.25–1.73 D/bohr.     

Theoretical dipole moment function of the X1Σ+ state of HI

Multiconfiguration self-consistent-field calculation has yielded the dipole moment function for the X¹Σ⁺ state of HI, which qualitatively confirms the experimental finding that the dipole derivative at R_e is negative. The calculated dipole moment for the v = 0 vibrational level is 0.665 D for both HI and DI as compared with the experimental values of 0.38 and 0.445 ± 0.02 D, respectively. The calculated potential curve yields values of R_e, D₀, and ΔG_v+1/2, in good agreement with spectroscopic data. A simple valence bond explanation has been provided for the qualitative difference between the dipole moment function of HI and those of the smaller hydrogen halides.     

The Electric Dipole Moment of the CO2–CO van der Waals Complex

Radiofrequency transitions withinK= 2 asymmetry doublets have been observed for the CO₂–CO van der Waals complex. A Stark effect measurement on theJ= 2,K= 2 transition provides an electric dipole moment of μ = 0.2493(1) D. Combining this result with the permanent moment of CO, μ_CO= 0.1098 D, gives a change of moment on complex formation of Δμ = 0.140 D. The sign of Δμ is such that the CO end of the complex is more positive than CO₂. The origin of Δμ should not be attributed to any single mechanism, and several different contributions to Δμ are discussed.     

Microwave spectrum and conformation of 6-thiabicyclo[3.1.0]hexane

The microwave spectrum of 6-thiabicyclo[3.1.0]hexane (cyclopentene sulfide) has been measured in the region 26,500-40,000 MHz. The experimental data are consistent with a single stable conformation. Furthermore, these data can only be satisfactorily explained by assuming that this conformation is the boat form. Rotational constants were obtained, both for the ground state and two excited vibrational states, while centrifugal distortion coefficients were obtained for the ground state and one excited vibrational state. The ground state rotational constants found were A₀ = 5026.243 ± 0.003 MHz, B₀ = 2833.813 ± 0.003 MHz, and C₀ = 2411.679 ± 0.03 MHz. For the ground state of the molecule, the electric dipole moment components were found to be μ_a = 1.800 ± 0.012 D and μ_c = 1.155 ± 0.024 D, yielding a total dipole moment μ = 2.139 ± 0.027 D.     

Temporal dependence of the dipole moment of long-wavelength forms of n-dimethylaminobenzonitrile

The temporal dependences μ_e(t) of the dipole moment of n-dimethylaminobenzonitrile excited to different states by quanta with different energies are evaluated based on the experimental correlation functions of the shift of instantaneous spectra. It is found that, upon excitation into the maximum of absorption, the relaxation changes of the spectra are accompanied by an increase in the dipole moment from 9 D in the Franck-Condon state to 16 D in the stationary state. At the same time, the excitation of luminescence at the red absorption edge by radiation at 403 nm leads to a decrease in the range of variation of the dipole moment. In this case, the initial value of the dipole moment amounts to 14 D and, during the lifetime of the excited state, it increases to 17 D. This indicates that the nature of the radiation excited at the wavelength 403 nm is directly related to internal charge transfer states of n-dimethylaminobenzonitrile.     

Dipole Moments of 4′-Aminoflavonol Fluorescent Probes in Different Solvents

Electrooptical absorption measurements (EOAM) were used to measure the dipole moments of the normal form of 4-(dimethylamino)-3-hydroxyflavone (FME), and 4 N-(15-azacrown-5)-3-hydroxyflavone (FCR) in 1,4-dioxane, toluene, and cyclohexane. With these probes excited-state intramolecular proton transfer (ESIPT) takes place. For comparison, the dipole moments of 4-(dimethylamino)-3-metoxyflavone (FME3ME), for which ESIPT is lacking, were measured, too. For all three probes the ground (_g) and excited Franck-Condon state (_e^FC) electrical dipole moments are parallel to each other and also parallel to the transition dipole moment. The electrical dipole moments of FCR, FME, and FME3ME in their ground state have values within the range (12.0–17.7) × 10^–30 C m. Upon optical excitation, the dipole moments increase by (41.9–52.9) ×10^–30 C m. The value of the change of the dipole moment vector ^a with excitation to the Franck-Condon state and the value of the vector _e^FC for FCR and FME are practically independent on the solvent polarity. From this point of view and due to large values of the dipole moments FCR and FME are very promising probes for the investigation of the distribution of the local polarity in biological systems using site-selective excitation of the different sites. Our steady-state fluorescence studies on FME and FCR have demonstrated a high spectral sensitivity of the normal form to such solvent characteristics as polarity.     

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.     

Ground and excited state dipole moments of coumarin 337 laser dye

This paper reports that the effects of spectral properties of coumarin 337 laser dye have been investigated in different solvents considering solvent parameters like dielectric constant (?) and refractive index (n) of different solvent polarities. The ground state (μ_g) and excited state (μ_e) dipole moments are calculated using Lippert's, Bakhshiev's, and Kawski-Chamma-Viallet's equations. In all these three equations the variation of Stokes shift was used to calculate the excited state (μ_e) dipole moment. It is observed that the Bakhshiev method is comparatively better than the other two methods for ground state and excited state dipole moment calculations. The angle between the excited state and ground state dipole moments is also calculated.     

The microwave spectrum, structure, chlorine nuclear quadrupole coupling constants, dipole moment, and centrifugal distortion constants of dichlorosilane

The microwave spectra of three isotopic species of dichlorosilane, SiH₂Cl₂, in its ground vibrational state, have been measured in the frequency region 8–40 GHz. The spectra have yielded values for the rotational constants, centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants, as well as the molecular dipole moment, 1.13 ± 0.02 D. The molecule has C_2v symmetry, and the bond lengths and angles r(Si---Cl=2.033±Å, r(Si---H)=1.480±0.015Å, (Cl---Si---Cl)=109°43′±20±, (H---Si---H)=111°18′±40′ The centrifugal distortion constants have been compared with those calculated using a published force field.     

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.     

Muon lifetimes and weak interaction coupling constants

Improvements in determining muon lifetimes that are possible with the pulsed muon beam at the ISIS accelerator complex near Oxford, UK, are examined. The requirements of the standard model do not require an improvement in (µ⁺)[G_µ], which is fortunate as the low repetition rate of ISIS make such difficult. However, for stopping µ^± in liquid hydrogen the differences [(µ⁺) –(µ^–, observing decay e^–)] and [(µ^–, e^–) – (µ^–, observing capture n)] can be well improved to give the induced pseudo-scalar coupling constant,g _P, to ±2% and hence the first test of the chiral structure of the nucleon.On leave from Department of Physics, William & Mary, VA, USA.     

Search for possible anapole and electric dipole moments of the proton on the basis of the pp ⇌ e+ e− annihilation reaction

Differential and total cross sections are found for the formation of an electron-positron pair during the annihilation of longitudinally polarized protons and antiprotons (pp e⁺ e^–) and for the inverse reaction (e⁺ e^- pp) in the single-photon approximation, account is taken of the anapole and electric dipole moments of the proton, which violate C, P, and T parity. Possible ways to determine the square moduli of the form factors for the anapole [G₁(q²)] and electric dipole [G₂(q²)] moments and to determine the relative phase of the form factors F_e(q²) and G₂(q²) [F_m(q²) and G₁(q²)] are pointed out. Estimates are found for ¦(G₁q²)¦² and ¦G₂(q²) ¦² with q² = –6.8 (GeV/c)².Translated from Izvestiya VUZ. Fizika, No. 8, pp. 59–65, August, 1970.The authors thank Professor A. A. Sokolov, Professor I. M. Ternov, and Yu. M. Loskutov for discussions of these results.     

Energy spectrum and angular distribution of muons from the decay of heavy leptons produced in colliding electron-positron beams

On the basis of an arbitrary (V, A) structure of the neutral weak ¯ee and LL currents (L=^–, M⁰) a study is made of the processes of production in colliding electron-positron beams of pairs of heavy leptons with subsequent decays in accordance with the schemes e⁺e^––(µ^–v_µv) + ⁺( anything) and e⁺e^–M⁰(µ^–e⁺v_e) + M⁰( anything). The energy spectrum and asymmetry of the distribution of the produced muons are investigated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 66–70, February, 1981.     

Line intensities of C2H2 in the 7.7 μm spectral region

Absolute intensities of 414 lines are measured in eight bands of the 7.7 μm spectral region of the ¹²C₂H₂ molecule, with an average accuracy of 5%. Vibrational transition dipole moment squared values and empirical Herman–Wallis coefficients are obtained in order to model the rotational dependence of the transition dipole moment squared, except for some forbidden bands for which smoothed values are given. These data are used to calculate a line list for atmospheric or astrophysical applications.     

Methyl and skeletal torsion interaction in methyl thiolfluoroformate

The microwave spectrum of methyl thiolfluoroformate (FCOSCH₃) is reported for the ground state and seven vibrational satellites. The methyl group is in the syn conformation to the carbonyl group. The dipole moment components are μ_a = 2.89(2) D, μ_b = 0.30(8) D, and μ_c = 0. Spacings of A and E levels due to methyl internal rotation are analyzed for the ground state, the first excited methyl torsional state, and the first excited skeletal torsional state. An anomalous sequence of A and E levels occurring in the latter satellite arises from torsional interaction, according to two-dimensional model calculations. Potential parameters consistent with the three observed level separations are V₃ = 304(5) cm⁻¹, V₆ = 23(1) cm⁻¹ for the methyl torsion and either k = 1.912 or k = 2.936 cm⁻¹ deg⁻² for the skeletal torsional force constant.     

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.     

High-Resolution Laser Spectroscopy of YbCl: The AΠ–XΣ Transition

The A²Π–X²Σ⁺ transition of ¹⁷⁴Yb³⁵Cl and ¹⁷²Yb³⁵Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0–0 and 1–0 bands with a measurement accuracy of approximately 0.0035 cm⁻¹. Resolved fluorescence was used to record the 0–1, 0–2, and 0–3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A²Π state are A_e = 1491.494(2) cm⁻¹ and R_e = 2.4433(1) Å, and for the X²Σ⁺ state, R_e = 2.4883(2) Å and γ_e = 4.59(2) × 10⁻³ cm⁻¹. The interaction between the X²Σ⁺ and A²Π states has been investigated and is shown to be the main contributor to the spin–rotation splitting in the ground state.     

“Artificial vacuum” for T-violation experiment

We point out the possible use of matrix isolation spectroscopy in experimental tests of fundamental physics. As a concrete example we show how this technique might be applied to measuring the T-violation electron electric dipole moment d_e. We estimate that a dipole moment could be detected down to d_e ∼ 6 × 10⁻²⁸e cm, in comparison to the current limit of d_e < 10⁻²⁴e cm.     

Measurement of the electric dipole moment of NO (X2 Π ν = 0,1) by mid-infrared laser magnetic resonance spectroscopy

A pair of parallel Stark plates are added to a CO laser magnetic resonance spectrometer to apply electric field in the absorption cell. This apparatus is used to measure the molecular electric dipole moment via Zeeman and Stark effects simultaneously. The saturated absorption spectra of NO (X²Π_3/2, ν = 1 ← 0) was observed and the electric dipole moments of NO were directly measured in the presence of an electric field. The dipole moments are determined as μ₀(ν = 0) = 0.1595(15) D, μ₁ (ν = 1) = 0.1425(16) D. The electric dipole moment of the vibrationally excited state (ν = 1) is determined for the first time. The dependence of the electric dipole moments on its nuclear distances is interpreted.