Kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 in the temperature range 220-360 K

The kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 have been studied in direct measurements at temperatures between 220 and 360 K using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated at 193 or 248 nm by pulsed laser photolysis of appropriate precursors. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of NO2 being in large excess over radical concentrations. The bimolecular rate coefficients of all three reactions are independent of the bath gas (He or N2) and pressure within the experimental range (1-6 Torr) and are found to depend on temperature as follows: k(CH2Cl + NO2) = (2.16 +/- 0.08) x 10(-11) (T/300 K)(-1.12+/-0.24) cm3 molecule(-1) s(-1) (220-363 K), k(CHCl2 + NO2) = (8.90 +/- 0.16) x 10(-12) (T/300 K)(-1.48+/-0.13) cm3 molecule(-1) s(-1) (220-363 K), and k(CCl3 + NO2) = (3.35 +/- 0.10) x 10(-12) (T/300 K)(-2.2+/-0.4) cm3 molecule(-1) s(-1) (298-363 K), with the uncertainties given as one-standard deviations. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are about +/-25%. In the reactions CH2Cl + NO2, CHCl2 + NO2, and CCl3 + NO2, the products observed are formaldehyde, CHClO, and phosgene (CCl2O), respectively. In addition, a weak signal for the HCl formation has been detected for the CHCl2 + NO2 reaction.     

Temperature-induced structural changes in glassy, supercooled, and molten silica from 77 to 2150 K

In situ polarized and depolarized Raman spectra of glassy, supercooled, and molten SiO2 have been measured over the broad temperature range 77-2150 K in an effort to examine possible structural changes caused by temperature variation. A new experimental setup using a CO2 laser for heating the sample has been designed allowing measurement with controllable blackbody radiation background at temperatures up to 2200 K. Careful and systematic relative intensity measurements and the use of the isotropic and anisotropic Raman representation of the spectra revealed hidden bands in the bending mode region and resolved bands in the stretching region of the spectra. Overall the spectra behavior shows similarities with the spectra of the recently studied tetrahedral glasses/melts of ZnCl2 and ZnBr2. Increasing temperature causes subtle changes of the relative intensities within the silicon-oxygen stretching region at approximately 750-850 cm(-1) and gives rise to a new band at approximately 930 cm(-1). The spectral behavior is interpreted to indicate that the "SiO42" tetrahedra are bound to each other to form the network by apex-bridging and partly by edge-bridging oxygens. The network structure of the glass/melt is formed by mixing a variety of tetrahedra participating in "open" (cristobalitelike), "cluster" (supertetrahedra), and "chain" edge-bridged substructures bound to each other by bridging oxygens. A weak in intensity but strongly polarized composite band is resolved at approximately 1400 cm(-1) and is assigned to Si[Double Bond]O terminal bond frequency. Temperature rise increases the concentration of the terminal bonds by breaking up the network. These structural changes are reminiscent of the polyamorphic transformations occurring in silica as has recently been predicted by computer simulations. At low frequencies the Raman spectra reveal the presence of the Boson peak at approximately 60 cm(-1) which is well resolved even above melting temperature up to 2150 K.     

Absolute band intensities in the nu19/nu23 (530 cm(-1)) and nu7 (777 cm(-1)) bands of acetone ((CH3)2CO) from 232 to 295 K

Absolute band intensities of acetone ((CH3)2CO) in the nu19/nu23 and nu7 band systems near 530 and 777 cm(-1), respectively, were measured at temperatures of 232, 262 and 295 K, using a Fourier transform infrared (FTIR) spectrometer. No evident temperature dependence for the band intensities was observed. The dipole moments and the fundamental band intensities were derived in the harmonic oscillator approximation. The results are useful for the spectroscopic retrieval of acetone concentrations in the upper atmosphere.     

Kinetics of the reactions of CH2I, CH2Br, and CHBrCl radicals with NO2 in the temperature range 220-360 K

The kinetics of the CH2I + NO2, CH2Br + NO2, and CHBrCl + NO2 reactions have been studied at temperatures between 220 and 360 K using laser photolysis/photoionization mass spectrometry. Decays of radical concentrations have been monitored in time-resolved measurements to obtain reaction rate coefficients under pseudo-first-order conditions. The bimolecular rate coefficients of all three reactions are independent of the bath gas (He or N2) and pressure within the experimental range (2-6 Torr) and are found to depend on temperature as follows: k(CH2I + NO2) = (2.18 +/- 0.07) x 10(-11) (T / 300 K)(-1.45) (+/- 0.22) cm3 molecule(-1) s(-1) (220-363 K), k(CH2Br + NO2) = (1.76 +/- 0.03) x 10(-11) (T/300 K)(-0.86) (+/- 0.09) cm3 molecule(-1) s(-1) (221-363 K), and k(CHBrCl + NO2) = (8.81 +/- 0.28) x 10(-12) (T/300 K)(-1.55) (+/- 0.34) cm3 molecule(-1) s(-1) (267-363 K), with the uncertainties given as one-standard deviations. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are about +/-25%. In the CH2I + NO2 and CH2Br + NO2 reactions, the observed product is formaldehyde. For the CHBrCl + NO2 reaction, the product observed is CHClO. In addition, I atom and iodonitromethane (CH2INO2) or iodomethyl nitrite (CH2IONO) formations have been detected for the CH2I + NO2 reaction.     

Determination of the rate constants for the NCO(X2Pi) + Cl(2P) and Cl(2P) + ClNCO(X1A') reactions at 293 and 345 K

The rate constant for the reaction of the isocyanato radical, NCO(X2Pi) with chlorine atoms, Cl(2P), has been measured at 293 +/- 2 and 345 +/- 3 K to be (6.9 +/- 3.8) x 10(-11) and (4.0 +/- 2.2) x 10(-11) cm3 molecules(-1) s,(-1) respectively, where the uncertainties include both random and systematic errors. The measurements were carried out at pressures of 1.3-6.2 Torr with either Ar or CF4 as the bath gas and were independent of both pressure and nature of the third body. Equal concentrations of NCO and Cl atoms were created by 248 nm photolysis of ClNCO. The reaction was monitored by following the temporal dependence of NCO(X2Pi) using time-resolved infrared absorption spectroscopy on rotational transitions of the NCO(10(1)1) <-- (00(1)0) combination band. The reaction rate constant was determined by using a simple chemical model and minimizing the sum of the residuals between the experimental and computer generated temporal NCO concentration profiles. The reaction Cl + ClNCO --> Cl2 + NCO was found to contribute to the observed NCO. The rate constant for this reaction was found to be (2.4 +/- 1.6) x 10(-13) and (1.9 +/- 1.2) x 10(-13) cm3 molecules(-1) s,(-1) at 293 and 345 K, respectively, where the uncertainties include both random and systematic error.     

Kinetics for the reactions of O- and O2- with O2(a1Deltag) measured in a selected ion flow tube at 300 K

The kinetics of the reactions of O- and O2- with O2(a1Deltag) have been studied at 300 K in a selected ion flow tube (SIFT). The O2(a1Deltag) concentrations have been determined using emission at 1270 nm from the O2(a1Deltag, v=0-->X3Sigmag-, v=0) transition measured with an InGaAs detector calibrated against absolute spectrally dispersed emission measurements. The rate constants measured for O- and O2- are 1.1x10(-10) and 6.6x10(-10) cm3 s-1, respectively, with uncertainties of +/-35%. The O2- reaction only produces electrons and can be described as Penning detachment, while the O- reaction has been found to produce both O2- and e-. The O2- branching fraction has a lower limit of approximately 0.30. Comparison of the present results to previous measurements found in the literature provides a resolution to a previous discrepancy in the rate constant values.     

The near infrared spectrum of ozone by CW-cavity ring down spectroscopy between 5850 and 7000 cm(-1): new observations and exhaustive review

Weak vibrational bands of (16)O(3) could be detected in the 5850-7030 cm(-1) spectral region by CW-cavity ring down spectroscopy using a set of fibered DFB diode lasers. As a result of the high sensitivity (noise equivalent absorption alpha(min) approximately 3 x 10(-10) cm(-1)), bands reaching a total of 16 upper vibrational states have been previously reported in selected spectral regions. In the present report, the analysis of the whole investigated region is completed by new recordings in three spectral regions which have allowed: (i) a refined analysis of the nu(1) + 3nu(2) + 3nu(3) band from new spectra in the 5850-5900 cm(-1) region; (ii) an important extension of the assignments of the 2nu(1)+5nu(3) and 4nu(1) + 2nu(2) + nu(3) bands in the 6500-6600 cm(-1) region, previously recorded by frequency modulation diode laser spectroscopy. The rovibrational assignments of the weak 4nu(1) + 2nu(2) + nu(3) band were fully confirmed by the new observation of the 4nu(1) + 2nu(2) + nu(3)- nu(2) hot band near 5866.9 cm(-1) reaching the same upper state; (iii) the observation and modelling of three A-type bands at 6895.51, 6981.87 and 6990.07 cm(-1) corresponding to the highest excited vibrational bands of ozone detected so far at high resolution. The upper vibrational states were assigned by comparison of their energy values with calculated values obtained from the ground state potential energy surface of (16)O(3). The vibrational mixing and consequently the ambiguities in the vibrational labelling are discussed. For each band or set of interacting bands, the spectroscopic parameters were determined from a fit of the corresponding line positions in the frame of the effective Hamiltonian (EH) model. A set of selected absolute line intensities was measured and used to derive the parameters of the effective transition moment operator. The exhaustive review of the previous observations gathered with the present results is presented and discussed. It leads to a total number of 3863 energy levels belonging to 21 vibrational states and corresponding to 7315 transitions. In the considered spectral region corresponding to up to 82% of the dissociation energy, the increasing importance of the "dark" states is illustrated by the occurrence of frequent rovibrational perturbations and the observation of many weak lines still unassigned.     

Rotationally resolved absorption cross sections of formaldehyde in the 28100-28500 cm(-1) (351-356 nm) spectral region: implications for in situ LIF measurements

The rotationally resolved ultraviolet absorption cross sections for the 2(0)(0)4(1)(0) vibrational band of the A(1)A(2)-X(1)A(1) electronic transition of formaldehyde (HCHO) at an apodized resolution of 0.027 cm(-1) (approximately 0.0003 nm at 352 nm) over the spectral range 28100-28500 cm(-1) (351-356 nm) at 298 and 220 K, using Fourier transform spectroscopy, are first reported here. Accurate rotationally resolved cross sections are important for the development of in situ HCHO laser-induced fluorescence (LIF) instruments and for atmospheric monitoring. Pressure dependence of the cross sections between 75 and 400 Torr at 298 K was explored, and an average pressure broadening coefficient in dry air of 1.8 x 10(-4) cm(-1) Torr(-1) for several isolated lines is reported. Gaseous HCHO was quantitatively introduced into a flow cell by evaporating micron-sized droplets of HCHO solution, using a novel microinjector technique. The condensed-phase concentrations of HCHO were determined by iodometric titrations to an accuracy of <1%. Accuracy of the measured absorption cross sections is estimated to be better than +/-5%. Integrated and differential cross sections over the entire band at low resolution (approximately 1 cm(-1)) obtained with our calibration technique are in excellent agreement with previous measurements. A maximum differential cross section of 5.7 x 10(-19) cm(2) molecule(-1) was observed at high resolution-almost an order of magnitude greater than any previously reported data at low resolution.     

Kinetics of the reactions of CH2Br and CH2I radicals with molecular oxygen at atmospheric temperatures

The kinetics of the reactions of CH2Br and CH2I radicals with O2 have been studied in direct measurements using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated by pulsed laser photolysis of appropriate precursors at 193 or 248 nm. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of O2 being in large excess over radical concentrations. No buffer gas density dependence was observed for the CH2I + O2 reaction in the range 0.2-15 x 10(17) cm(-3) of He at 298 K. In this same density range the CH2Br + O2 reaction was obtained to be in the third-body and fall-off area. Measured bimolecular rate coefficient of the CH2I + O2 reaction is found to depend on temperature as k(CH2I + O2)=(1.39 +/- 0.01)x 10(-12)(T/300 K)(-1.55 +/- 0.06) cm3 s(-1)(220-450 K). Obtained primary products of this reaction are I atom and IO radical and the yield of I-atom is significant. The rate coefficient and temperature dependence of the CH2Br + O2 reaction in the third-body region is k(CH2Br + O2+ He)=(1.2 +/- 0.2)x 10(-30)(T/300 K)(-4.8 +/- 0.3) cm6 s(-1)(241-363 K), which was obtained by fitting the complete data set simultaneously to a Troe expression with the F(cent) value of 0.4. Estimated overall uncertainties in the measured reaction rate coefficients are about +/-25%.     

Molecular magnetic properties of two-copper(II) containing complexes [Cu(II) (1-phenylamidino-O-n-butylurea) en (H2O)]2(2+) and [Cu(II) sulphato-mono (1-phenylamidino-O-methylurea)]2. An EPR study

Electron paramagnetic resonance (EPR) investigations were conducted on [Cu(II) (1-phenylamidino-O-n-butylurea) en (H2O)]2(2+) (1) and [Cu(II) sulphato-mono (1-phenylamidino-O-methylurea)]2 (2) respectively, in the temperature range 300-77K. Fine structure characteristics of S = 1 system, was observed in both complexes with zero field splitting of 0.0525 and 0.0225 cm(-1), respectively, suggesting the formation of dimeric complexes. The presence of the half-field signal (DeltaMs= +/-2), in the complex 1, further confirmed the formation of dimer. The temperature dependence of EPR signal intensity has given evidence for the ferromagnetic (FM) coupling between the two Cu2+ ions. The isotropic exchange interaction constants J, were evaluated from this and were found out to be approximately 57 and approximately 27 cm(-1), respectively, for the complexes 1 and 2. The photoacoustic spectra of these complexes had shown a band around 26,400 cm(-1) characteristic of metal-metal bonding giving an independent support for the existence of dimeric Cu2+ species. The high magnetic moment values at room temperature for complex 1 (2.68 microB) and complex 2 (2.00 microB), obtained from the magnetic susceptibility measurements, support the formation of ferromagnetically coupled Cu2+ dimers.     

Yield of electronically excited CN molecules from the dissociative recombination of HNC+ with electrons

The authors have studied CN(B-X) and CN(A-X) emissions produced by the dissociative recombination of HNC+ ions with thermal electrons in a flowing afterglow experiment. A separate drift tube study showed that the reaction Ar(+)+HCN, the precursor reaction used in the flow-tube experiment, produces predominantly HNC+ rather than the more energetic HCN+ isomer. Models simulating the ion-chemical processes, diffusion, and gas mixing in the afterglow plasma were fitted to observed position dependent CN(A-X) and CN(B-X) band intensities. Absolute yields of CN(B) and CN(A) were then obtained by comparing the CN band intensities to those of CO bands produced by recombination of CO(2) (+) ions. It was concluded that the 300 K recombination coefficient of HNC+ is close to 2 x 10(-7) cm(3) s(-1), that CN(B) is formed with a yield of 0.22+/-0.08 and CN(A) with a yield of 0.14+/-0.05. By comparison to synthetic spectra, the rotational temperature of CN(B) was estimated to be approximately 2500 K. It was also found that recombination produces CN(B) and CN(A) with far greater vibrational excitation than would be expected from the "impulse model" of Bates [Mon. Not. R. Astron. Soc. 263, 369 (1993)].     

Temperature dependence of exciton diffusion in conjugated polymers

The temperature dependence of the exciton dynamics in a conjugated polymer is studied using time-resolved spectroscopy. Photoluminescence decays were measured in heterostructured samples containing a sharp polymer-fullerene interface, which acts as an exciton quenching wall. Using a 1D diffusion model, the exciton diffusion length and diffusion coefficient were extracted in the temperature range of 4-293 K. The exciton dynamics reveal two temperature regimes: in the range of 4-150 K, the exciton diffusion length (coefficient) of approximately 3 nm (approximately 1.5 x 10 (-4) cm2/s) is nearly temperature independent. Increasing the temperature up to 293 K leads to a gradual growth up to 4.5 nm (approximately 3.2 x 10 (-4) cm2/ s). This demonstrates that exciton diffusion in conjugated polymers is governed by two processes: an initial downhill migration toward lower energy states in the inhomogenously broadened density of states, followed by temperature activated hopping. The latter process is switched off below 150 K.     

Ion core structure in (C(2)n+ and (CS2)n- (n=3-10) studied by infrared photodissociation spectroscopy

Infrared photodissociation spectra of (CS(2))(n) (+) and (CS(2))(n) (-) with n=3-10 are measured in the 1100-2000 cm(-1) region. All the (CS(2))(n) (+) clusters exhibit three bands at approximately 1410, approximately 1490, and approximately 1540 cm(-1). The intensity of the 1540 cm(-1) band relative to those of the other bands increases with increasing the cluster size, indicating that the band at 1540 cm(-1) is assignable to the antisymmetric CS stretching vibration of solvent CS(2) molecules in the clusters. On the basis of density functional theory calculations, the 1410 and 1490 cm(-1) bands of (CS(2))(n) (+) are assigned to CS stretching vibrations of the C(2)S(4) (+) cation core with a C(2) form. The (CS(2))(n) (-) clusters show two bands at around 1215 and 1530 cm(-1). Similar to the case of cation clusters, the latter band is ascribed to the antisymmetric CS stretching vibration of solvent CS(2) molecules. Vibrational frequency analysis of CS(2) (-) and C(2)S(4) (-) suggests that the 1215 cm(-1) band is attributed to the antisymmetric CS stretching vibration of the CS(2) (-) anion core with a C(2v) structure.     

A range of spin-crossover temperature T1/2>300 K results from out-of-sphere anion exchange in a series of ferrous materials based on the 4-(4-imidazolylmethyl)-2-(2-imidazolylmethyl)imidazole (trim) ligand, [Fe(trim)2]X2 (X=F, Cl, Br, I): comparison of experimental results with those derived from density functional theory calculations

The synthesis and characterization of [FeII(trim)2]Cl2 (2), [FeII(trim)2]Br2MeOH (3), and [FeII(trim)2]I2MeOH (4), including the X-ray crystal structure determinations of 2 (50 and 293 K) and 4 (293 K), have been performed and their properties have been examined. In agreement with the magnetic susceptibility results, the M?ssbauer data show the presence of high-spin (HS) to low-spin (LS) crossover with a range of T1/2 larger than 300 K (from approximately 20 K for [FeII(trim)2]F2 (1) to approximately 380 K for 4). All complexes in this series include the same [Fe(trim)2]2+ complex cation: the ligand field comprises a constant contribution from the trim ligands and a variable one originating from the out-of-sphere anions, which is transmitted to the metal center by the connecting imidazole rings and hydrogen bonds. The impressive variation in the intrinsic characteristics of the spin-crossover (SCO) phenomenon in this series is then interpreted as an inductive effect of the anions transmitted to the nitrogen donors through the hydrogen bonds. Based on this qualitative analysis, an increased inductive effect of the out-of-sphere anion corresponds to a decreased SCO temperature T1/2, in agreement with the experimental results. Electronic structure calculations with periodic boundary conditions have been performed that show the importance of intermolecular effects in tuning the ligand field, and thus in determining the transition temperature. Starting with the geometries obtained from the X-ray studies, the [FeII(trim)2]X2 complex molecules 1-4 have been investigated both for the single molecules and the crystal lattices with the local density approximation of density functional theory. The bulk geometries of the complex cations deduced from the X-ray studies and those calculated are in fair agreement for both approaches. However, the trend observed for the transition temperatures of 1-4 disagrees with the trend for the spin-state splittings ES (difference EHS-ELS between the energy of the HS and LS isomers) calculated for the isolated molecules, whereas it agrees with the trend for ES calculated with periodic boundary conditions. The latter calculations predict the strongest stabilization of the HS state for the fluoride complex, which actually is essentially HS above T=50 K, while the most pronounced stabilization of the LS state is predicted for 4, in line with the experimental results.     

The 1.28 μm transparency window of methane (7541-7919 cm⁻¹): empirical line lists and temperature dependence (80 K-300 K)

The high sensitivity absorption spectra of methane at room temperature and 80 K were recorded by CW-Cavity Ring Down Spectroscopy in the 1.28 μm transparency window (7541-7919 cm(-1)). The empirical line parameters of 7690 and 5794 transitions were retrieved at room temperature and at 80 K, respectively. The achieved sensitivity (α(min)≈ 10(-10) cm(-1)) allowed detecting transitions with intensities as small as 5 × 10(-30) cm per molecule. In order to facilitate identification of the CH(3)D transitions present in the CRDS spectrum of methane in "natural" isotopic abundance, the spectrum of a highly enriched CH(3)D sample was recorded by differential absorption spectroscopy at room temperature and at 80 K. The CH(3)D relative contribution in the considered transparency window is found to be significant only at 80 K (up to 15%) but more limited than in the 1.58 μm transparency window.The low energy values of the transitions observed at both room temperature and 80 K were derived from the variation of their line intensities. Empirical lower states and J values have been obtained for 2821 CH(4) transitions representing 94.1 and 98.5% of the absorbance in the region at room temperature and 80 K, respectively. The good quality of these derived energy values is demonstrated by the marked propensity of the corresponding CH(4) lower state J values to be close to integers. The constructed line lists extend to higher energies the WKC (Wang-Kassi-Campargue) line lists of methane in the near infrared (1.71-1.26 μm). They allow one accounting for the temperature dependence of methane absorption between 80 K and 300 K and are of importance for the analysis of the near infrared spectrum of several planetary bodies like Titan, Uranus and Neptune. The centers of the 3ν(2) + ν(3) and 6ν(4) bands responsible of the absorption in the studied region are discussed in relation with recent theoretical calculations.     

The absorption spectrum of D2: ultrasensitive cavity ring down spectroscopy of the (2-0) band near 1.7 μm and accurate ab initio line list up to 24,000 cm(-1)

Eleven very weak electric quadrupole transitions Q(2), Q(1), S(0)-S(8) of the first overtone band of D(2) have been measured by very high sensitivity CW-cavity ring down spectroscopy (CRDS) between 5850 and 6720 cm(-1). The noise equivalent absorption of the recordings is on the order of α(min) ≈ 3 × 10(-11) cm(-1). By averaging a high number of spectra, the noise level was lowered to α(min) ≈ 4 × 10(-12) cm(-1) in order to detect the S(8) transition which is among the weakest transitions ever detected in laboratory experiments (line intensity on the order of 1.8 × 10(-31) cm/molecule at 296 K). A Galatry profile was used to reproduce the measured line shape and derive the line strengths. The pressure shift and position at zero pressure limit were determined from recordings with pressures ranging between 10 and 750 Torr. A highly accurate theoretical line list was constructed for pure D(2) at 296 K. The intensity threshold was fixed to a value of 1 × 10(-34) cm/molecule at 296 K. The obtained line list is provided as supplementary material. It extends up to 24,000 cm(-1) and includes 201 transitions belonging to ten v-0 cold bands (v = 0-9) and three v-1 hot bands (v = 1-3). The energy levels include the relativistic and quantum electrodynamic corrections as well as the effects of the finite nuclear mass. The quadrupole transition moments are calculated using highly accurate adiabatic wave functions. The CRDS line positions and intensities of the first overtone band are compared to the corresponding calculated values and to previous measurements of the S(0)-S(3) lines. The agreement between the CRDS and theoretical results is found within the claimed experimental uncertainties (on the order of 1 × 10(-3) cm(-1) and 2% for the positions and intensities, respectively) while the previous S(0)-S(3) measurements showed important deviations for the line intensities.     

Rate coefficients for the OH + HC(O)C(O)H (glyoxal) reaction between 210 and 390 K

Rate coefficients, k1(T), over the temperature range of 210-390 K are reported for the gas-phase reaction OH + HC(O)C(O)H (glyoxal) --> products at pressures between 45 and 300 Torr (He, N2). Rate coefficients were determined under pseudo-first-order conditions in OH using pulsed laser photolysis production of OH radicals coupled with OH detection by laser-induced fluorescence. The rate coefficients obtained were independent of pressure and bath gas. The room-temperature rate coefficient, k1(296 K), was determined to be (9.15 +/- 0.8) x 10-12 cm3 molecule-1 s-1. k1(T) shows a negative temperature dependence with a slight deviation from Arrhenius behavior that is reproduced over the temperature range included in this study by k1(T) = [(6.6 +/- 0.6) x 10-18]T2[exp([820 +/- 30]/T)] cm3 molecule-1 s-1. For atmospheric modeling purposes, a fit to an Arrhenius expression over the temperature range included in this study that is most relevant to the atmosphere, 210-296 K, yields k1(T) = (2.8 +/- 0.7) x 10-12 exp[(340 +/- 50)/T] cm3 molecule-1 s-1 and reproduces the rate coefficient data very well. The quoted uncertainties in k1(T) are at the 95% confidence level (2sigma) and include estimated systematic errors. Comparison of the present results with the single previous determination of k1(296 K) and a discussion of the reaction mechanism and non-Arrhenius temperature dependence are presented.     

Electrodeless determination of the trap density, decay kinetics, and charge separation efficiency of dye-sensitized nanocrystalline TiO(2)

We have studied photoinduced charge separation in a bare, 3.4 microm thick layer of nanocrystalline ("nc") anatase TiO(2) and an nc-TiO(2) layer coated with free-base 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin (H(2)TPPC) using the electrodeless flash-photolysis time-resolved microwave-conductivity technique (FP-TRMC). Photoconductivity transients, resulting from the formation of mobile, conduction band electrons in the semiconductor have been measured on excitation with 3 ns pulses of UV (300 nm) and visible (410-700 nm) light. The product of the yield of formation of mobile charge carriers, phi, and the sum of their mobilities, Sigmamicro, has been determined from the maximum conductivity for light intensities varying from approximately 10(12) to approximately 10(16) photons/cm(2)/pulse. For the bare nc-TiO(2) layer at 300 nm and the coated layer at all wavelengths, phiSigmamicro initially increased with increasing intensity, reached a maximum, and eventually decreased at high intensities. The initial increase is attributed to the gradual filling of (surface) electron trapping sites. This effect was absent when the samples were continuously illuminated with background irradiation at 300 nm with an intensity of 6 x 10(13) photons/cm(2)/s (40 microW/cm(2)), thereby presaturating the trapping sites prior to the laser pulse. The trap-free mobility of electrons within these 9 nm nanoparticles is estimated to be 0.034 cm(2)/Vs at 9 GHz. The eventual decrease in phiSigmamicro at intensities corresponding to an electron occupancy of more than one electron per particle is unaffected by background illumination, and is attributed to a decrease in micro due to electron-electron interactions within the semiconductor particles. The photoconductivity action spectrum of the coated nc-TiO(2) layer closely followed the photon attenuation spectrum in the visible of the porphyrin, with a charge separation efficiency per absorbed photon of 18% at the Soret band maximum. The after-pulse decay of the photoconductivity showed a power law behavior over a time scale of nanoseconds to several hundreds of microseconds, which is attributed to multiple trapping and detrapping events at chemical or physical defects within the semiconductor matrix.     

Micro-Raman observation on the HPO4(2-) association structures in an individual dipotassium hydrogen phosphate (K2HPO4) droplet

A single K(2)HPO(4) droplet with size of ～50 μm on a Teflon substrate was forced to enter into the supersaturated state by decreasing the relative humidity (RH), allowing accurate control over the concentration of the solute within a droplet of a nanogram. The K(2)HPO(4) solutions from dilute (0.1-1.0 mol·L(-1) bulk) to concentrated state (a droplet from RH 98.2% to 25.1%) were studied through micro-Raman spectroscopy in the spectral region of about 200-4000 cm(-1). The area ratio between the water stretching band to the sum of the ν(1)-PO(3), ν(2)-POH, and ν(4)-PO(3) bands of the HPO(4)(2-) at various RHs was used to describe the dehydration behavior of a microsized single K(2)HPO(4) droplet in dehumidifying process. The peak position of the v(1)-PO(3) band for the 1 mol·L(-1) bulk solution appeared at 991 cm(-1) and moved to 986 cm(-1) at 98.2% RH, to 978 cm(-1) at 70.2% RH, and then to 964 cm(-1) at 30.0% RH for a droplet, accompanying an increase of the full width at half-height (fwhh) of this peak from 16.3 to 17.2, 22.2, and then to 24.2 cm(-1), indicating transition of the HPO(4)(2-) anions from monomers to dimers/trimers/oligomers and then to polyanions with chain structures in the K(2)HPO(4) solutions. After 25.1% RH, the solid was proved to be K(2)HPO(4)·3H(2)O according to the Raman spectral features. Furthermore, the O-H stretching envelope of a K(2)HPO(4) droplet showed that the intensity ratios of the strong hydrogen bonding component (3255 cm(-1)) to the weak one (3417 cm(-1)) and the cage-like water (2925 cm(-1)) to the weak one (3417 cm(-1)) were sensitive to the HPO(4)(2-) association structures, which can be used to understand the effects of dimers/trimers/oligomers and chain structures of the HPO(4)(2-) associations on the hydrogen bonding of water molecules.     

Overtone dissociation of peroxynitric acid (HO2NO2): absorption cross sections and photolysis products

Band strengths for the second (3nuOH) and third (4nuOH) overtones of the OH stretch vibration of peroxynitric acid, HO2NO2 (PNA) in the gas-phase were measured using Cavity Ring-Down Spectroscopy (CRDS). Both OH overtone transitions show diffuse smoothly varying symmetrical absorption profiles without observable rotational structure. Integrated band strengths (base e) at 296 K were determined to be S(3nuOH) = (5.7 +/- 1.1) x 10(-20) and S(4nuOH) = (4.9 +/- 0.9) x 10(-21) cm(2) molecule(-1) cm(-1) with peak cross sections of (8.8 +/- 1.7) x 10(-22) and (7.0 +/- 1.3) x 10(-23) cm(2) molecule(-1) at 10086.0 +/- 0.2 cm(-1) and 13095.8 +/- 0.4 cm(-1), respectively, using PNA concentrations measured on line by Fourier-transform infrared and ultraviolet absorption spectroscopy. The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors in the measurements. OH overtone spectra measured at lower temperature, 231 K, showed a narrowing of the 3nuOH band along with an increase in its peak absorption cross section, but no change in S(3nuOH) to within the precision of the measurement (+/-9%). Measurement of a PNA action spectrum showed that HO2 is produced from second overtone photodissociation. The action spectrum agreed with the CRDS absorption spectra. The PNA cross sections determined in this work for 3nuOH and 4nuOH will increase calculated atmospheric photolysis rates of PNA slightly.