Relaxation in torsional motion of triplet oxirane

The rotational barrier height E_rot in the lowest triplet state oxirane molecule was calculated to be 26.3 kcal/mole using a double zeta basis set with partial geometry optimization. This suggest ldrelaxedrd rotation and the computed e(T₁- E(S_o) + E_rot value is commensurate with the enthalpy change for the oxirane-forming O(³P) + C₂H₄ reaction, thus providing a rationale for the stereochemical features of the reaction.     

On the OH torsional motion in solid pentachlorophenol

After theoretical and experimental studies, an assignment is made at 409 cm^?1 for the OH torsional vibration in solid pentachlorophenol. An optimization method is applied to calculate the V₂ torsional barrier, which provides larger values than those obtained from the conventional methods used by other authors.     

Crystalline structure and OH torsional motion in calcium-strontium arsenate apatites

The crystalline structure of Ca_10?xSr_x(AsO₄)₆(OH)₂ has been studied, and the lattice parameters determined. It has been found that the unit cell expands with x. Geometric parameters of the unit cell, which are defined in relation to the hindered rotation of the OH group around the c axis, have been also obtained. From the ir data, the torsional potential function has been calculated in first and second approximations. A method for computing that function in any order approximation is given. A semiempirical curve is found, relating the stretching and torsional motions for both the OH and OD groups.     

Spectral broadening in quantum dots-sensitized photoelectrochemical solar cells based on CdSe and Mg-doped CdSe nanocrystals

In order to absorb a broad spectrum in visible region, a co-sensitized TiO₂ electrode was prepared by CdSe and Mg-doped CdSe quantum dots (Q dots). The power conversion efficiency of the co-sensitized Q dots photoelectrochemical solar cells (PECs) showed 1.03% under air mass 1.5 condition (I = 100 mW/cm²), which is higher than that of individual Q dots-sensitized PECs. The incident-photon-to-current conversion efficiency of the co-sensitized PECs showed absorption peaks at 541 and 578 nm corresponding to the two Q dots and displayed a broad spectral response over the entire visible spectrum in the 500–600 nm wavelength domains.     

Spectral diffusion in a fluctuating charge model of water

We apply the combined electronic structure/molecular dynamics approach of Corcelli, Lawrence, and Skinner [J. Chem. Phys. 120, 8107 (2004)] to the fluctuating charge (SPC-FQ) model of liquid water developed by Rick, Stuart, and Berne [J. Chem. Phys. 101, 6141 (1994)]. For HOD in H(2)O the time scale for the long-time decay of the OD stretch frequency time-correlation function, which corresponds to the time scale for hydrogen-bond rearrangement in the liquid, is about 1.5 ps. This result is significantly longer than the 0.9 ps decay previously calculated for the nonpolarizable SPC/E water model. Our results for the SPC-FQ model are in better agreement with recent vibrational echo experiments.     

Anomalous splittings of torsional sublevels induced by the aldehyde inversion motion in the S1 state of acetaldehyde

The G6 group-theoretical high-barrier formalism developed previously for internally rotating and inverting CH3NHD is used to interpret the abnormal torsional splittings in the S1 state of acetaldehyde for levels 14(0-)15(0), 14(0-)15(1), and 14(0-)15(2), where 14(0-) denotes the upper inversion tunneling component of the aldehyde hydrogen and 15 denotes the methyl torsional vibration. This formalism, derived using an extended permutation-inversion group G6m, treats simultaneously methyl torsional tunneling, aldehyde-hydrogen inversion tunneling and overall rotation. Fits to the rotational states of the four pairs of inversion-torsion vibrational levels (14(0+)15(0A,E), 14(0-)15(0A,E)), (14(0+)15(1A,E), 14(0-)15(1A,E)), (14(0+)15(2A,E), 14(0-)15(2A,E)), and (14(0+)15(3A,E), 14(0-)15(3A,E)) are performed, giving root-mean-square deviations of 0.003, 0.004, 0.004, and 0.004 cm(-1), respectively, which are nearly equal to the experimental uncertainty of 0.003 cm(-1). For torsional levels lying near the top of the torsional barrier, this theoretical model, after including higher-order terms, provides satisfactory fits to the experimental data. The partially anomalous K-doublet structure of the S1 state, which deviates from that in a simple torsion-rotation molecule, is fitted using this formalism and is shown to arise from coupling of torsion and rotation motion with the aldehyde-hydrogen inversion.     

Spectral diffusion in the tunneling spectra of ligand-stabilized undecagold clusters

We report diffusion in the tunneling spectra of isolated, ligand-stabilized undecagold (Au11) clusters immobilized by attachment to alpha,omega-alkanedithiolate tethers inserted into alkanethiolate self-assembled monolayers. We use scanning tunneling microscopy and spectroscopy at cryogenic (UHV, 4 K) conditions to measure these clusters' conductance with complete control of their chemical and physical environment; additionally, thermal broadening of their electronic states as well as their mobility is minimized. At low temperature, the Au11 clusters demonstrate Coulomb blockade behavior, with zero-conductance gaps resulting from quantum size effects. Surprisingly, chemically identical and even single particles produced different families of tunneling spectra, comparable to previous results for heterogeneous distributions of particles. We hypothesize that, while these particles are chemically attached to the surface of the SAM for measurement, these assemblies may still be sufficiently dynamic to affect their transport properties significantly.     

Molecules with large-amplitude torsional motion partially oriented in a nematic liquid crystal: ethane and isotopomers

An NMR study on ethane and five isotopomers dissolved in the nematic liquid crystal Merck ZLI 1132 is performed. A consistent set of dipolar and quadrupolar couplings is obtained. The dipolar couplings are corrected for harmonic vibrational effects, while the contribution from the torsional motion is incorporated classically. The corrected dipolar couplings cannot be understood in terms of a reasonable molecular structure unless effects of the reorientation-vibration interaction are taken into account. Assuming that the reorientation-vibration contributions that are known for the methyl group in methyl fluoride are transferable to ethane, excellent agreement between observed and calculated dipolar couplings is obtained on the basis of the ethane gas-phase structure. The observed and calculated deuterium quadrupolar couplings show discrepancies supporting the notion that average electric field gradients are important in liquid-crystal solvents. An important consequence of the transferability of the reorientation-vibration correlation is that in other molecules with a methyl group the same procedure as for ethane can be followed. Inclusion of this effect generally removes the need to interpret changes in observed dipolar couplings in terms of elusive chemical effects.     

Meta conjugation effect on the torsional motion of aminostilbenes in the photoinduced intramolecular charge-transfer state

The photochemical behavior of a series of trans-3-(N-arylamino)stilbenes (m1, aryl = 4-substituted phenyl with a substituent of cyano (CN), hydrogen (H), methyl (Me), or methoxy (OM)) in both nonpolar and polar solvents is reported and compared to that of the corresponding para isomers (p1CN, p1H, p1Me, and p1OM). The distinct propensity of torsional motion toward a low-lying twisted intramolecular charge-transfer (TICT) state from the planar ICT (PICT) precursor between the meta and para isomers of 1CN and 1Me reveals the intriguing meta conjugation effect and the importance of the reaction kinetics. Whereas the poor charge-redistribution (delocalization) ability through the meta-phenylene bridge accounts for the unfavorable TICT-forming process for m1CN, it is such a property that slows down the decay processes of fluorescence and photoisomerization for m1Me, facilitating the competition of the single-bond torsional reaction. In contrast, the quinoidal character for p1Me in the PICT state kinetically favors both fluorescence and photoisomerization but disfavors the single-bond torsion. The resulting concept of thermodynamically allowed but kinetically inhibited TICT formation could also apply to understanding the other D-A systems, including trans-4-cyano-4'-(N,N-dimethylamino)stilbene (DCS) and 3-(N,N-dimethylamino)benzonitrile (3DMABN).     

Binary diffusion coefficients of phenolic compounds in subcritical water using a chromatographic peak broadening technique

Infinite dilution diffusion coefficients of certain phenolic compounds were measured as a function of temperature in water slightly acidified with formic acid using the Taylor dispersion method. The diffusion coefficients calculated using the chromatographic peak broadening technique were found to increase exponentially with an increase in the temperature. The diffusion coefficients of the selected phenolic compounds did not vary as a function of their molecular weights and the diffusion coefficients of the phenolic compounds increased as a function of temperature (from 2.16 × 10⁻¹⁰ m² s⁻¹ at 298 K to 5.79 × 10⁻¹⁰ m² s⁻¹ at 413 K for malvidin-3,5-diglucoside). However, for some phenolic compounds such as gallic acid monohydrate, quercetin-3-β-d-glucoside, protocatechuic acid and (−)-epicatechin, there were difficulties in making measurements above temperatures of 352 K, 372 K, 392 K and 413 K, respectively, due to thermal degradation of the phenolic compounds in water above these temperatures. The experimentally measured diffusion coefficients of the phenolic compounds were correlated as a function of temperature and solvent viscosity and were compared with those predicted using theoretical models. The validity of the Stokes-Einstein diffusion model in predicting the diffusion coefficients of the phenolic compounds in hot pressurized water was also evaluated.     

Growth and motion of heterogeneous water droplets in laminar flow diffusion chambers

The growth of heterogeneous water droplets containing nanoparticles is studied in two laminar flow diffusion chambers of different designs. It is shown that the efficiency of heterogeneous condensation is, to a substantial extent, governed by the processes of heat and mass transfer inside a chamber condenser. Integral parameter C(R) representing the probability that a nanoparticle with radius R is covered with a condensate film in a laminar flow chamber is calculated. It is established that, in air-water vapor mixtures, the radius of heterogeneous water droplets may amount to several micrometers and efficient condensation begins on spherical nanoparticles when their radii exceed 5 nm.     

Spectral and spin diffusion in stationary saturation of ESR spectra of paramagnetic centers

Theoretical and experimental approaches have been taken in a study of the feasibility of using the method of stationary saturation of ESR spectra in studying processes of dipole relaxation of paramagnetic centers in magnetically dilute solids. In the example of a system consisting of two kinds of paramagnetic centers, relaxation characteristics have been formulated by the stationary saturation method and the electron spin-echo method. It has been established that, with certain limitations and the use of a correct workup of the experiment, the stationary saturation method can be applied successfully in determining the relaxation characteristics of paramagnetic centers and features of their spatial position. Results obtained by this method are discussed in the example of systems in which electron-nucleus interaction makes a substantial contribution to the phase relaxation process.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 520–528, September–October, 1989.     

Band broadening evaluation by back-and-forth capillary electrophoresis

The purpose of this study is to develop a method for precise evaluation of band broadening in capillary electrophoresis. A capillary electrophoresis system with on-column twin detectors is constructed. Back-and-forth electrophoresis permits zones to make a round trip between the twin detectors placed at distant positions on the capillary. The system is capable of eliminating extra-column effects and discriminating between reversible and irreversible band-broadening mechanisms.     

Quantification of PCB by dechlorination to biphenyl

Summary Since polychlorinated biphenyls (PCB) are widespread biologically active contaminants in the environment, the need of a sensitive, rapid and simple screening-method for control purposes is obvious. The dechlorination of PCB to biphenyl with LiAlH₄ and subsequent quantification by HPLC and UV detection may fulfil these requirements. Results achieved with this dechlorination method are compared with those obtained by packed-column or capillary-column gas chromatography and EC detection.

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Bestimmung von PCB durch Dechlorierung zu Biphenyl

Zusammenfassung Das ubiquitäre Vorkommen von polychlorierten Biphenylen (PCB) als Kontaminantien in unserer Umwelt erfordert eine empfindliche, rasche und einfache Screening-Methode. Dechlorierung der PCB mit LiAlH₄ zu Biphenyl und anschließende Quantifizierung mittels HPLC und UV-Detektion erfüllt diese Forderungen. Analysenresultate der beschriebenen Dechlorierungsmethode werden verglichen mit Resultaten der Gas-Chromatographie an gepackten Säulen und Capillarsäulen mit EC-Detektion.

     

Low temperature pressure broadening of OCS by He

We report experimentally measured cross sections for pressure broadening of OCS by He from 4.2 to 23 K. These measurements were made in a quasiequilibrium cell using the collisional cooling technique. Cross sections were obtained for the broadening of the J=2<--1, J=3<--2, and J=4<--3 rotational transitions of OCS. Theoretical cross sections were also calculated using a recent He-OCS potential surface. While at the higher temperatures, approximately 20 K, there is only modest disagreement between experiment and theory, this disagreement increases steadily with decreasing temperature, with predicted cross sections rising steeply while the experimental data remains constant or decreases slightly. Comparisons to similar recent experimental studies are made and reasons for the observed discrepancy between experiment and theory are considered.     

Observation of the neutron quasi-elastic broadening by polymers in soluttion

The quasi-elastic neutron scattering peaks obtained from polytetrahydrofuran and its perdeutero analogue have been observed in solution in CS₂. Thus the incoherent and coherent components can be separated. The results do not support the Rouse model of polymer chain dynamics but the Zimm model, which includes hydrodynamic interactions, may apply.     

Abnormal broadening in triplet-to-triplet absorption spectra caused by aromatic solvents

The triplet-triplet absorption spectra of a number of aromatic molecules were shown to be broadened in low temperature matrices formed by aromatic solvents (toluene, 4-isopropylbiphenyl) as compared with those in aliphatic solvents (ethanol, methylcyclohexane, triethylamine). The effect is exponentially dependent on the energy of the upper triplet state of the solute molecule. The phenomenon is discussed in terms of a strong exchange-resonance interaction between the triplet states of solute and solvent.     

First passage times for a tracer particle in single file diffusion and fractional Brownian motion

We investigate the full functional form of the first passage time density (FPTD) of a tracer particle in a single-file diffusion (SFD) system whose population is: (i) homogeneous, i.e., all particles having the same diffusion constant and (ii) heterogeneous, with diffusion constants drawn from a heavy-tailed power-law distribution. In parallel, the full FPTD for fractional Brownian motion [fBm-defined by the Hurst parameter, H ∈ (0, 1)] is studied, of interest here as fBm and SFD systems belong to the same universality class. Extensive stochastic (non-Markovian) SFD and fBm simulations are performed and compared to two analytical Markovian techniques: the method of images approximation (MIA) and the Willemski-Fixman approximation (WFA). We find that the MIA cannot approximate well any temporal scale of the SFD FPTD. Our exact inversion of the Willemski-Fixman integral equation captures the long-time power-law exponent, when H ≥ 1/3, as predicted by Molchan [Commun. Math. Phys. 205, 97 (1999)] for fBm. When H < 1/3, which includes homogeneous SFD (H = 1/4), and heterogeneous SFD (H < 1/4), the WFA fails to agree with any temporal scale of the simulations and Molchan's long-time result. SFD systems are compared to their fBm counter parts; and in the homogeneous system both scaled FPTDs agree on all temporal scales including also, the result by Molchan, thus affirming that SFD and fBm dynamics belong to the same universality class. In the heterogeneous case SFD and fBm results for heterogeneity-averaged FPTDs agree in the asymptotic time limit. The non-averaged heterogeneous SFD systems display a lack of self-averaging. An exponential with a power-law argument, multiplied by a power-law pre-factor is shown to describe well the FPTD for all times for homogeneous SFD and sub-diffusive fBm systems.