RESUMEN
Produced by both nature and human activities, sulfur dioxide (SO2) is an important species in the earth's atmosphere. SO2 has also been found in the atmospheres of other planets and satellites in the solar system. The photoabsorption cross sections and photodissociation of SO2 have been studied for several decades. In this paper, we reported the experimental results for photodissociation dynamics of SO2 via the GÌ1B1 state. By analyzing the images from the time-sliced velocity map ion imaging method, the vibrational state population distributions and anisotropy parameters were obtained for the O(1D2) + SO(X3Σ-, a1Δ, b1Σ+) and O(1S0) + SO(X3Σ-) channels, and the branching ratios for the channels O(1D2) + SO(X3Σ-), O(1D2) + SO(a1Δ), and O(1D2) + SO(b1Σ+) were determined to be â¼0.3, â¼0.6, and â¼0.1, respectively. The SO products were dominant in electronically and rovibrationally excited states, which may have yet unrecognized roles in the upper planetary atmosphere.
RESUMEN
The wavelength-dependent dynamics of the O(1D2) channel, formed by photoexcitation of CO2 to the 1Δu state at 143.53-153.03 nm, is investigated by using the time-sliced velocity-mapped ion imaging method. The measured ionic peaks of the O(1D2) images are analyzed to determine the total kinetic energy release (TKER) spectra and image anisotropy parameters. The structures observed in the TKER spectra can be directly assigned to the ro-vibrational state distributions of the counter CO photofragments. Compared to those observed at 157 and 155 nm, the highly rotationally excited CO photofragments still obviously appear in v = 0 and 1, but the fraction of rotational excitations is significantly reduced. Conversely, the CO photofragments exhibit substantially higher vibrational excitations, implying that the nearly linear 21A' state also contributes to dissociation in addition to the bend configuration. The image anisotropy parameters display an extremely slow decreasing trend with an increase of the CO ro-vibrational state besides those for the highest ro-vibrationally excited CO photofragments. Nevertheless, the nonaxial recoil effect, suggested in previous photodissociation studies of CO2 and other triatomic molecular systems, is still appropriate to explain the observations of internal energy dependences of image anisotropy parameters.
RESUMEN
Photodissociation of CO2 via the 1Πg state is investigated using a time-sliced velocity-mapped ion imaging apparatus combined with a tunable vacuum ultraviolet photolysis source. The main O(1D2) + CO(X1Σ+) channel is directly observed from the measured images of O(1D2) photoproducts at 129.08-134.76 nm. The total kinetic energy release spectra determined based on these images show that the energetic thresholds for the O(1D2) + CO(X1Σ+) photoproducts correspond to the thermochemical thresholds for the photodissociation of CO2(v2 = 0) and CO2(v2 = 1). One significant difference among the CO(X1Σ+, v) vibrational distributions for the predominant CO2(v2 = 0) dissociation is that the population of CO(v = 0) becomes favorable at 130.23-133.45 nm compared to the Boltzmann-like component (v > 0) that always exists at 129.08-134.76 nm. The wavelength dependences of the overall ß are found to follow the variation trend of the CO(v = 0) abnormal intensity. The vibrational state-specific ß values present a roughly decreasing trend with an increase in v, whereas ß(v = 0) appears to be significantly larger than ß(v = 1) at 130.23-133.45 nm compared to 134.76 and 129.08 nm. The non-statistical CO(v = 0) with larger ß values at 130.23-133.45 nm implies that an additional pathway may open through the conical intersection coupling to the dissociative 21A' state, except for the ever-existing pathway that yields the Boltzmann-like component. In contrast, at 129.08 nm, the restoration of the statistical equilibrium in the CO(X1Σ+, v) vibrational distribution may be caused by the emergence of novel dissociation pathways arising from the participation of the 31Aâ³ state.
RESUMEN
In a two-dimensional (2D) metallic nanostructure, when a sample's thickness is shorter than a carrier mean free path, the ultrathin thickness may influence carrier and energy transport, owing to surface scattering. However, to date, for metallic 2D transition-metal carbides (MXenes), experiments and calculations related to surface scattering have not been performed. The contribution of ultrathin structures to carrier surface scattering in MXene is yet to be explored. Herein, to reveal this effect, we design various models, including metal/MXene, dielectric/MXene, and bulk structure, and analyze their carrier dynamics via ultrafast spectroscopy. The results related to carrier dynamics indicate that the influence of the dielectric/MXene interface and the temperature is negligible. In contrast, the carrier dynamic lifetimes are prolonged owing to weakened surface scattering in metal/MXene, which is supported by ab initio calculations. These results suggest that the carrier-phonon scattering is dominated by surface scattering. These findings can help guide effective energy transport and enhance energy conversion and catalysis.
RESUMEN
The state-resolved photodissociation of NO2via the 12B2 and 22B2 excited states has been investigated by using time-sliced velocity-mapped ion imaging technique. The images of the O(3PJ=2,1,0) products at a series of excitation wavelengths are measured by employing a 1 + 1' photoionization scheme. The total kinetic energy release (TKER) spectra, NO vibrational state distributions and anisotropy parameters (ß) are derived from the O(3PJ=2,1,0) images. For the 12B2 state photodissociation of NO2, the TKER spectra mainly present a non-statistical vibrational state distribution of the NO co-products, and the profiles of most vibrational peaks display a bimodal structure. The ß values show a gradual decrease with the photolysis wavelength increasing except for a sudden increase at 357.38 nm. The results suggest that the NO2 photodissociation via the 12B2 state proceeds via the non-adiabatic transition between the 12B2 and XÌ2A1 states, leading to the NO(X2Π) + O(3PJ) products with wavelength-dependent rovibrational distributions. As for photodissociation of NO2via the 22B2 state, the NO vibrational state distribution is relatively narrow with the main peak shifting from v = 1, 2 at 235.43-249.22 nm to v = 6 at 212.56 nm. The ß values exhibit two distinctly different angular distributions, i.e., near isotropic at 249.22 and 246.09 nm and anisotropic at the rest of the excitation wavelengths. These results are consistent with the fact that the 22B2 state potential energy surface has a barrier, and the dissociation process is fast when the initial populated level is above this barrier. A bimodal vibrational state distribution is clearly observed at 212.56 nm, in which the main distribution (peaking at v = 6) is ascribed to dissociation via an avoided crossing with the higher electronically excited state while the subsidiary distribution (peaking at v = 11) likely arises due to dissociation via the internal conversion to the 12B2 state or to the XÌ ground state.
RESUMEN
Understanding vacuum ultraviolet photodissociation dynamics of Carbonyl sulfide (OCS) is of considerable importance in the study of atmospheric chemistry. Yet, photodissociation dynamics of the CS(X1Σ+) + O(3Pj=2,1,0) channels following excitation to the 21Σ+(ν1',1,0) state has not been clearly understood so far. Here, we investigate the O(3Pj=2,1,0) elimination dissociation processes in the resonance-state selective photodissociation of OCS between 147.24 and 156.48 nm by using the time-sliced velocity-mapped ion imaging technique. The total kinetic energy release spectra are found to exhibit highly structured profiles, indicative of the formation of a broad range of vibrational states of CS(1Σ+). The fitted CS(1Σ+) vibrational state distributions differ for the three 3Pj spin-orbit states, but a general trend of the inverted characteristics is observed. Additionally, the wavelength-dependent behaviors are also observed in the vibrational populations for CS(1Σ+, v). The CS(X1Σ+, v = 0) has a significantly strong population at several shorter wavelengths, and the most populated CS(X1Σ+, v) is gradually transferred to a higher vibrational state with the decrease in the photolysis wavelength. The measured overall ß-values for the three 3Pj spin-orbit channels slightly increase and then abruptly decrease as the photolysis wavelength increases, while the vibrational dependences of ß-values show an irregularly decreasing trend with increasing CS(1Σ+) vibrational excitation at all studied photolysis wavelengths. The comparison of the experimental observations for this titled channel and the S(3Pj) channel reveals that two different intersystem crossing mechanisms may be involved in the formation of the CS(X1Σ+) + O(3Pj=2,1,0) photoproducts via the 21Σ+ state.
RESUMEN
We study the vacuum ultraviolet (VUV) photodissociation dynamics of carbonyl sulfide (OCS) by using the time sliced velocity map ion imaging technique. Experimental images of the dissociative O (3PJ=0,1,2) products were acquired at five VUV photolysis wavelengths from 133.26 to 139.96 nm that correspond to the F Rydberg state of OCS. High vibrational states of the carbon monosulfide (CS) co-products are partially resolved in the images. The product total kinetic energy releases, angular distributions, and the product state branching ratios were derived from the experimental images. Notably, it is found that the anisotropic parameters change systematically with the photolysis wavelength. The anisotropic parameters and the product state branching ratios are significantly sensitive to the J quantum number of the O (3PJ) products. The phenomenon indicates that multiple nonadiabatic pathways are strongly involved in the photodissociation processes.
RESUMEN
Typical extension flow occurs in electrospinning process of Poly(vinylidene fluoride) (PVDF) solutions such that researchers focus on extensional rheological behaviors of PVDF solutions. The extensional viscosity of PVDF solutions is measured to know the fluidic deformation in extension flows. The solutions are prepared by dissolving PVDF powder into N,N-dimethylformamide (DMF) solvent. A homemade extensional viscometric device is used to produce uniaxial extension flows and the feasibility of the viscometric device is verified by applying the glycerol as a test fluid. Experimental results show that PVDF/DMF solutions are extension shinning as well as shear shinning. The Trouton ratio of thinning PVDF/DMF solution is close to three at very low strain rate and then reaches a peak value until it drops to a small value at high strain rate. Furthermore, an exponential model may be used to fit the measured values of uniaxial extensional viscosity at various extension rates, while traditional power-law model is applicable to steady shear viscosity. For 10~14% PVDF/DMF solution, the zero-extension viscosity by fitting reaches 31.88~157.53 Pa·s and the peak Trouton ratio is 4.17~5.16 at applied extension rate of less than 34 s-1. Characteristic relaxation time is λ~100 ms and corresponding critical extension rate is εËc~5 s-1. The extensional viscosity of very dilute PVDF/DMF solution at very high extension rate is beyond the limit of our homemade extensional viscometric device. This case needs a higher sensitive tensile gauge and a higher-accelerated motion mechanism for test.
RESUMEN
The spin-forbidden O(3P2) + CO(X1Σ+, v) channel formed from the photodissociation of CO2 in the low energy band centered at 148 nm is investigated by using the time-sliced velocity-mapped ion imaging technique. The vibrational-resolved images of the O(3P2) photoproducts measured in the photolysis wavelength range of 144.62-150.45 nm are analyzed to give the total kinetic energy releases (TKER) spectra, CO(X1Σ+) vibrational state distributions, and anisotropy parameters (ß). The TKER spectra reveal the formation of correlated CO(X1Σ+) with well resolved v = 0-10 (or 11) vibrational bands. Several high vibrational bands that were observed in the low TKER region for each studied photolysis wavelength exhibit a bimodal structure. The CO(X1Σ+, v) vibrational distributions all present inverted characteristics, and the most populated vibrational state changes from a low vibrational state to a relatively higher vibrational state with a change in the photolysis wavelength from 150.45 to 144.62 nm. However, the vibrational-state specific ß-values for different photolysis wavelengths present a similar variation trend. The measured ß-values show a significant bulge at the higher vibrational levels, in addition to the overall slow decreasing trend. The observed bimodal structures with mutational ß-values for the high vibrational excited state CO(1Σ+) photoproducts suggest the existence of more than one nonadiabatic pathway with different anisotropies in the formation of O(3P2) + CO(X1Σ+, v) photoproducts across the low energy band.
RESUMEN
The photodissociation of OCS is necessary to model the primary photochemical processes of OCS in the global cycling of sulfur and interstellar photochemistry. Here, by combining the time-sliced velocity-map ion imaging technique with the single vacuum ultraviolet photon ionization method, we have studied the CO(1Σ+, v) + S(1D2) photoproduct channel from the OCS photodissociation via the eight different vibrational resonances ( = 1-8) in the 21Σ+(, 1, 0) â X1Σ+(0, 0, 0) band. From the measured S(1D2) images, the wavelength-dependent CO(1Σ+, v) vibrational state populations have been obtained in the wavelength range of 142.98-154.37 nm. The majority of the CO(1Σ+, v) photoproducts are shown to abruptly populate from low vibrational states to high vibrational states as the photolysis wavelength decreases from 152.38 to 148.92 nm. The anisotropy parameters (ß) for the CO(1Σ+, v) + S(1D2) channel have also been determined from the images of the S(1D2) photoproducts. It is found that the vibrational state-specific ß-values present a similar decreasing trend with increasing CO vibrational excitation for all the eight vibrational resonances of OCS*(21Σ+). These observations indicate that there is a possibility that more than one non-adiabatic dissociation pathways with different dissociation lifetimes are involved in the formation of CO(1Σ+) + S(1D2) photoproducts from the initial vibronic levels of the 21Σ+ state to the final dissociative state.
RESUMEN
The rotational state resolved photodissociation dynamics of D2O via the CÌ(010) state has been investigated by using the D-atom Rydberg tagging time-of-flight technique combined with a tunable vacuum ultraviolet light source. The D-atom action spectrum of the CÌ(010) â XÌ(000) band and the corresponding time-of-flight (TOF) spectra of D-atom photoproducts formed following the excitation of D2O to individual rotational transition have been measured. By comparison with the action spectrum of the CÌ(000) â XÌ(000) band, the bending vibrational constant of the CÌ state for D2O can be determined to be v2 = 1041.37 ± 0.71 cm-1. From the TOF spectra, the product kinetic energy spectra, the vibrational state distributions of OD products, and the state resolved anisotropy parameters have been determined. The experimental results indicate a dramatic variation in the OD product state distributions for different rotational excitations. This illuminates that there are two distinctive coupling channels from the CÌ(010) state to the low-lying electronic states: the homogeneous electronic coupling to the Ã1B1 state, resulting in vibrationally hot OD(X) products, and the Coriolis-type coupling to the BÌ1A1 state, producing vibrationally cold but rotationally hot OD(X) and OD(A) products. Furthermore, the three-body dissociation channel is confirmed, which is attributed to the CÌ â 1A2 or CÌ â Ã pathway. In comparison with the previous results of D2O photolysis via the CÌ(000) state, it is found that the v2 vibration of the parent molecule enhances both the vibrational and rotational excitations of OD products.
RESUMEN
The vacuum ultraviolet (VUV) photodissociation of CO2 is important to understand the primary photochemical processes of CO2 induced by solar VUV excitation in the Earth's atmosphere. Here, we report a detailed study of vibrational-state-specific photodissociation dynamics of the CO(X1Σ+) + O(1D2) channel via the 3P1Πu state by using the time-sliced velocity-mapped ion imaging apparatus combined with the single VUV photoionization detection scheme. By recording the sliced images of the O(1D2) photoproducts formed by VUV photoexcitation of CO2 to the individual vibrational structure of the 3P1Πu state, both the vibrational state distributions of the counterpart CO(X1Σ+) photoproducts and the vibrational-state-specific product anisotropy parameters (ß) are determined. The experimental results show that photodissociation of CO2 at 108.22, 107.50, 106.10, and 104.76 nm yields less anisotropic (ß > 0) and inverted distributed CO(X1Σ+, v) photoproducts. The possible dissociation mechanism for the CO(X1Σ+) + O(1D2) channel may involve the non-adiabatic transition of excited CO2* from the initially prepared state to the 31A' state with potential energy barriers. While at 108.82 and 107.35 nm, the vibrational distributions are found to have the population peaked at a low vibrational state, and the anisotropy parameters turn out to be negative. Such variation indicates the possibility of another non-adiabatic dissociation pathway that may involve Coriolis-type coupling to the low-lying dissociative state. These observations show sclear evidence of the influence of the initially vibrational excitations on the photodissociation dynamics of CO2 via the 3P1Πu state.
RESUMEN
Hydrogen chloride (HCl) contributes substantially to the atmospheric Cl; both species could affect the composition of Earth's atmosphere and the fate of pollutants. Here, we present the kinetics study for syn-CH3CHOO reaction with HCl using experimental measurement and theoretical calculations. The experiment was conducted in a flow tube reactor at a pressure of 10 Torr and temperatures ranging from 283 to 318 K by using the OH laser-induced fluorescence (LIF) method. Transition-state theory and quantum chemistry calculations with QCISD(T) were used to calculate the rate coefficients. Weak negative temperature dependence was observed with a measured activation energy of -(2.98 ± 0.12) kcal mol-1 and a calculated zero-point-corrected barrier energy of -3.29 kcal mol-1. At 298 K, the rate coefficient was measured to be (4.77 ± 0.95) × 10-11 cm3 s-1, which was in reasonable agreement with 2.2 × 10-11 cm3 s-1 from the theoretical calculation.
RESUMEN
The excited-state decay dynamics of 2-ethylpyrrole following UV excitation in the wavelength range of 254.8-218.0 nm is investigated in detail using the femtosecond time-resolved photoelectron imaging method. The time-resolved photoelectron spectra and photoelectron angular distributions at all pump wavelengths are carefully analysed and the following picture is derived: at the longest pump wavelengths (254.8, 248.3 and 246.1 nm), 2-ethylpyrrole is excited to the S1(1πσ*) state having a lifetime of about 50 fs. At 248.3, 246.1 and 237.4 nm, another excited state of Rydberg character is excited. The lifetime of this state is â¼570 fs at 237.4 nm and becomes slightly longer at other two pump wavelengths. At the shortest pump wavelengths (230.8 and 218.0 nm), 2-ethylpyrrole is excited to a state which is tentatively assigned to the 11ππ* state, having a lifetime of 75 ± 15 and 48 ± 10 fs for the longer and shorter pump wavelengths, respectively. Internal conversion to the S1(1πσ*) state might be one of the decay mechanisms of the 11ππ* state.
RESUMEN
The state-resolved photodissociation of the CO(1Σ+) + S(1S0) photoproduct channel, formed by vacuum ultraviolet photoexcitation of OCS to a progression of the symmetric stretching vibration (ν1') in the E and F states, has been investigated by using the time-sliced velocity map ion imaging technique. The total kinetic energy release spectra and the vibrational state specific anisotropy parameters (ß) were obtained based on the raw images of S(1S0) photoproducts detected in the wavelength ranges of 134.40-140.98 nm, respectively. Except for vibrational band origins, the CO(1Σ+) photoproducts are found to have more significant populations at highly vibrationally excited states as the symmetric stretching vibrational excitation of the E and F states increases. Furthermore, the vibrational-state specific ß values for the CO(1Σ+) + S(1S0) channel via the E and F states both show a sudden change from negative to positive in the vicinity of moderately vibronic levels of the E and F states. This anomalous phenomenon suggests that multiple excited states with different symmetries are involved in the photoexcitation process at relatively short photolysis wavelengths due to the strong vibronic couplings existing in the higher vibronic levels of the E and F states, and the formation of CO(1Σ+) + S(1S0) photoproducts may proceed by different nonadiabatic interactions from the prepared excited states to the lower dissociative state 1Σ+, with strong dependence of the initially symmetric stretching excitation in the Rydberg-type transitions.
RESUMEN
It has long been known that there is a conical intersection (CI) between the ground and first excited electronic state in the H3 system. Its associated geometric phase (GP) effect has been theoretically predicted to exist below the CI since a long time. However, the experimental evidence has not been established yet and its dynamical origin is waiting to be elucidated. Here we report a combined crossed molecular beam and quantum reactive scattering dynamics study of the H+HD â H2+D reaction at 2.28 eV, which is well below the CI. The GP effect is clearly identified by the observation of distinct oscillations in the differential cross section around the forward direction. Quantum dynamics theory reveals that the GP effect arises from the phase alteration of a small part of the wave function, which corresponds to an unusual roaming-like abstraction pathway, as revealed by quasi-classical trajectory calculations.
RESUMEN
Vacuum ultraviolet photodissociation dynamics of carbonyl sulfide (OCS) was investigated by using the time-sliced velocity map ion imaging technique. Images of the S(1SJ=0) and S(3PJ=2,1,0) photofragments formed in the OCS photodissociation were acquired at six photolysis wavelengths from 147.24 to 156.48 nm. Vibrational states of the CO coproducts were partially resolved and identified in the images. Two main dissociation product channels, namely, the spin-allowed S(1SJ=0) + CO(X1Σg+) and spin-forbidden S(3PJ=2,1,0) + CO(X1Σg+), were observed. At each photolysis wavelength, the total kinetic energy releases, the relative population of different CO vibrational states, and the anisotropic parameters were derived. Variations of the relative population were noticed between different spin-orbit states of the S(3PJ) channel. It was found that the S(1SJ=0) + CO(X1Σg+) channel is dominated by the 1Σ+ â 1Σ+ parallel transition of OCS. Interestingly, two types of anisotropic parameters are found at different photolysis wavelengths for the spin-forbidden S(3PJ=2,1,0) + CO(X1Σg+) product channel. The anisotropic parameters at 147.24 and 150.70 nm are significantly smaller than at the other four photolysis wavelengths. This phenomenon indicates two different nonadiabatic pathways are responsible for the spin-forbidden channels, which is consistent with the barrier structure in the exit channel of one of the triplet states.
RESUMEN
Hydrogen sulfide radicals in the ground state, SH(X), and hydrogen disulfide molecules, H2S, are both detected in the interstellar medium, but the returned SH(X)/H2S abundance ratios imply a depletion of the former relative to that predicted by current models (which assume that photon absorption by H2S at energies below the ionization limit results in H + SH photoproducts). Here we report that translational spectroscopy measurements of the H atoms and S(1D) atoms formed by photolysis of jet-cooled H2S molecules at many wavelengths in the range 122 ≤ λ ≤155 nm offer a rationale for this apparent depletion; the quantum yield for forming SH(X) products, Γ, decreases from unity (at the longest excitation wavelengths) to zero at short wavelengths. Convoluting the wavelength dependences of Γ, the H2S parent absorption and the interstellar radiation field implies that only ~26% of photoexcitation events result in SH(X) products. The findings suggest a need to revise the relevant astrochemical models.
RESUMEN
State-to-state photodissociation of carbon dioxide (CO2) via the 3p1Πu Rydberg state was investigated by the time-sliced velocity map ion imaging technique (TSVMI) using a tunable vacuum ultraviolet free electron laser (VUV FEL) source. Raw images of the O(1S) products resulting from the O(1S) + CO(X1Σ+) channel were acquired at the photolysis wavelengths between 107.37 and 108.84 nm. From the vibrational resolved O(1S) images, the product total kinetic energy releases and the vibrational state distributions of the CO(X1Σ+) co-products were obtained, respectively. It is found that vibrationally excited CO co-products populate at as high as v = 6 or 7 while peaking at v = 1 and v = 4, and most of the individual vibrational peaks present a bimodal rotational structure. Furthermore, the angular distributions at all studied photolysis wavelengths have also been determined. The associated vibrational-state specific anisotropy parameters (ß) exhibit a photolysis wavelength-dependent feature, in which the ß-values observed at 108.01 nm and 108.27 nm are more positive than those at 107.37 nm and 107.52 nm, while the ß-values have almost isotropic behaviour at 108.84 nm. These experimental results indicate that the initially prepared CO2 molecules around 108 nm should decay to the 41A' state via non-adiabatic coupling, and dissociate in the 41A' state to produce O(1S) + CO(X1Σ+) products with different dissociation time scales.
RESUMEN
Photodissociation dynamics of H2O and D2O via the D[combining tilde] state by one-photon excitation have been investigated using the H/D atom Rydberg tagging time-of-flight technique. The TOF spectra of the H/D-atom product in both parallel and perpendicular polarizations have been measured. Product translational energy distributions and angular distributions have been derived from TOF spectra. By simulating these distributions, quantum state distributions of the OH/OD product as well as the state-resolved angular anisotropy parameters were determined. The most important pathway of H2O/D2O dissociation via the D[combining tilde] state leads to highly rotationally excited OH/OD(X, v = 0) products, while vibrationally excited OH/OD products with v≥ 1 comprise only one third of the total OH/OD(X) population. The branching ratios of OH(A)/OH(X) and OD(A)/OD(X) have also been determined, 1.0/3.0 for H2O at 122.12 nm and 1.0/2.2 for D2O at 121.95 nm, which are reasonably consistent with the values predicted by the previous theory.