ABSTRACT
The COVID-19 pandemic illustrates how the impacts of climate change are beginning to converge with other developing challenges with a likely peak with global population, requiring more integrated responses locally, regionally and globally.
ABSTRACT
Phenol is an important model molecule for the theoretical and experimental investigation of dissociation in the multistate potential energy surfaces. Recent theoretical calculations [X. Xu et al., J. Am. Chem. Soc. 136, 16378 (2014)] suggest that the phenoxyl radical produced in both the X and A states from the O-H bond fission in phenol can contribute substantially to the slow component of photofragment translational energy distribution. However, current experimental techniques struggle to separate the contributions from different dissociation pathways. A new type of time-resolved pump-probe experiment is described that enables the selection of the products generated from a specific time window after molecules are excited by a pump laser pulse and can quantitatively characterize the translational energy distribution and branching ratio of each dissociation pathway. This method modifies conventional photofragment translational spectroscopy by reducing the acceptance angles of the detection region and changing the interaction region of the pump laser beam and the molecular beam along the molecular beam axis. The translational energy distributions and branching ratios of the phenoxyl radicals produced in the X, A, and B states from the photodissociation of phenol at 213 and 193 nm are reported. Unlike other techniques, this method has no interference from the undissociated hot molecules. It can ultimately become a standard pump-probe technique for the study of large molecule photodissociation in multistates.
ABSTRACT
The dynamics of the (18)O((3)P) + (32)O2 isotope exchange reaction were studied using crossed atomic and molecular beams at collision energies (E(coll)) of 5.7 and 7.3 kcal/mol, and experimental results were compared with quantum statistical (QS) and quasi-classical trajectory (QCT) calculations on the O3(X(1)A') potential energy surface (PES) of Babikov et al. [D. Babikov, B. K. Kendrick, R. B. Walker, R. T. Pack, P. Fleurat-Lesard, and R. Schinke, J. Chem. Phys. 118, 6298 (2003)]. In both QS and QCT calculations, agreement with experiment was markedly improved by performing calculations with the experimental distribution of collision energies instead of fixed at the average collision energy. At both collision energies, the scattering displayed a forward bias, with a smaller bias at the lower E(coll). Comparisons with the QS calculations suggest that (34)O2 is produced with a non-statistical rovibrational distribution that is hotter than predicted, and the discrepancy is larger at the lower E(coll). If this underprediction of rovibrational excitation by the QS method is not due to PES errors and/or to non-adiabatic effects not included in the calculations, then this collision energy dependence is opposite to what might be expected based on collision complex lifetime arguments and opposite to that measured for the forward bias. While the QCT calculations captured the experimental product vibrational energy distribution better than the QS method, the QCT results underpredicted rotationally excited products, overpredicted forward-bias and predicted a trend in the strength of forward-bias with collision energy opposite to that measured, indicating that it does not completely capture the dynamic behavior measured in the experiment. Thus, these results further underscore the need for improvement in theoretical treatments of dynamics on the O3(X(1)A') PES and perhaps of the PES itself in order to better understand and predict non-statistical effects in this reaction and in the formation of ozone (in which the intermediate O3* complex is collisionally stabilized by a third body). The scattering data presented here at two different collision energies provide important benchmarks to guide these improvements.
ABSTRACT
Near-edge X-ray absorption fine structure (NEXAFS) spectra of phenyl ether at the carbon K-edge and 1,3-diphenoxybenzene at both the carbon and oxygen K-edges were measured in the total ion yield mode using X-rays from a synchrotron and a reflectron time-of-flight mass spectrometer. Time-dependent density functional theory was adopted to calculate the carbon and oxygen K-edge NEXAFS spectra of phenol, phenyl ether, and 1,3-diphenoxybenzene. The assignments and a comparison of the experimental and calculated spectra are presented. The mass spectra of ionic products formed after X-ray absorption at various excitation energies are also reported. Specific dissociations were observed for the 1s â π* transition of phenyl ether. In comparison with phenol and phenyl ether, the dependence of the fragmentation on the excitation site and destination state was weak in 1,3-diphenoxybenzene, likely as a result of delocalization of the valence electrons and rapid randomization of energy.
ABSTRACT
A time-of-flight mass spectrometer with orthogonal acceleration and soft X-rays from synchrotron radiation were utilized to measure near-edge X-ray absorption fine structure (NEXAFS) spectra of carbon and oxygen in phenol and the corresponding ionic fragments following core excitation. The photon energies were in the range of 284-298 eV for the carbon K-edge and 529.5-554.5 eV for the oxygen K-edge. The total ion yield, ion intensity for each ionic fragment, and ion intensity ratio, defined as ion intensity divided by total ion yield, were measured as a function of photon energy. Possible mechanisms of dissociation are proposed and enhancements of specific products of dissociation are reported. In general, the enhancement of these specific products is small in the carbon K-edge region but is clear for some products at the oxygen K-edge. In particular, elimination of the H atom from the hydroxyl group was observed only at the oxygen K-edge. One remarkable result is that an excitation of a core-level electron of oxygen greatly enhanced the cleavage of specific C-C bonds.
ABSTRACT
RATIONALE: In most previous studies, the ratios of desorbed ions and neutrals from matrix-assisted laser desorption/ionization (MALDI) were measured outside the common MALDI conditions. In this work, we measured the ratios under common MALDI conditions. METHODS: Ions were detected using a time-of-flight mass spectrometer in combination with a time-gated ion imaging detector. Mass-resolved desorbed neutral molecules at different angles and velocities were measured using a modified crossed molecular beam apparatus. RESULTS: The upper limit of the ion-to-neutral ratio from pure 2,5-dihydroxybenzoic acid (25DHB) is 4 × 10(-9) at laser fluence 40 J/m(2), it increases to 3 × 10(-7) at laser fluence 250 J/m(2). The ratios of matrix from the mixture of 25DHB and analyte remain in the same order of magnitude as pure 25DHB. However, the ratio of analyte depends strongly on the analyte. Values as large as 10(-3)-10(-4) for bradykinin and as small as <10(-8) for glycine were observed at laser fluence ~100 J/m(2). CONCLUSION: The ion-to-neutral ratios of 25DHB matrix measured in this work are much smaller than some of the values reported in previous work using different methods and/or under different MALDI conditions.
Subject(s)
Gentisates/chemistry , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization , Equipment Design , Ions/chemistry , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization/instrumentationABSTRACT
The products and dynamics of the reactions (18)O((3)P)+NO(2) and (18)O((1)D)+NO(2) have been investigated using crossed beams and provide new constraints on the structures and lifetimes of the reactive nitrogen trioxide intermediates formed in collisions of O((3)P) and O((1)D) with NO(2). For each reaction, two product channels are observed - isotope exchange and O(2)+NO formation. From the measured product signal intensities at collision energies of â¼6 to 9.5 kcal/mol, the branching ratio for O(2)+NO formation vs. isotope exchange for the O((3)P)+NO(2) reaction is 52(+6/-2)% to 48(+2/-6)%, while that for O((1)D)+NO(2) is 97(+2/-12)% to 3(+12/-2)%. The branching ratio for the O((3)P)+NO(2) reaction derived here is similar to the ratio measured in previous kinetics studies, while this is the first study in which the products of the O((1)D)+NO(2) reaction have been determined experimentally. Product energy and angular distributions are derived for the O((3)P)+NO(2) isotope exchange and the O((1)D)+NO(2)âO(2)+NO reactions. The results demonstrate that the O((3)P)+NO(2) isotope exchange reaction proceeds by an NO(3)∗ complex that is long-lived with respect to its rotational period and suggest that statistical incorporation of the reactant (18)O into the product NO(2) (apart from zero point energy isotope effects) likely occurs. In contrast, the (18)O((1)D)+NO(2)âO(2)+NO reaction proceeds by a direct "stripping" mechanism via a short-lived (18)O-O-NO∗ complex that results in the occurrence of (18)O in the product O(2) but not in the product NO. Similarly, (18)O is detected in O(2) but not NO for the O((3)P)+NO(2)âO(2)+NO reaction. Thus, even though the product energy and angular distributions for O((3)P)+NO(2)âO(2)+NO derived from the experimental data are uncertain, these results for isotope labeling under single collision conditions support previous kinetics studies that concluded that this reaction proceeds by an asymmetric (18)O-O-NO∗ intermediate and not by a long-lived symmetric NO(3)∗ complex, as earlier bulk isotope labeling experiments had concluded. Applicability of these results to atmospheric chemistry is also discussed.
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The photodissociation of gaseous benzaldehyde (C(6)H(5)CHO) at 193, 248, and 266 nm using multimass ion imaging and step-scan time-resolved Fourier-transform infrared emission techniques is investigated. We also characterize the potential energies with the CCSD(T)/6-311+G(3df,2p) method and predict the branching ratios for various channels of dissociation. Upon photolysis at 248 and 266 nm, two major channels for formation of HCO and CO, with relative branching of 0.37:0.63 and 0.20:0.80, respectively, are observed. The C(6)H(5)+HCO channel has two components with large and small recoil velocities; the rapid component with average translational energy of approximately 25 kJ mol(-1) dominates. The C(6)H(6)+CO channel has a similar distribution of translational energy for these two components. IR emission from internally excited C(6)H(5)CHO, ν(3) (v=1) of HCO, and levels v≤2, J≤43 of CO are observed; the latter has an average rotational energy of approximately 13 kJ mol(-1) and vibrational energy of approximately 6 kJ mol(-1). Upon photolysis at 193 nm, similar distributions of energy are observed, except that the C(6)H(5)+HCO channel becomes the only major channel with a branching ratio of 0.82±0.10 and an increased proportion of the slow component; IR emission from levels ν(1) (v=1) and ν(3) (v=1 and 2) of HCO and v≤2, J≤43 of CO are observed; the latter has an average energy similar to that observed in photolysis at 248 nm. The observed product yields at different dissociation energies are compared to statistical-theory predicted results based on the computed singlet and triplet potential-energy surfaces.
Subject(s)
Chemistry/trends , Science/trends , Chemistry/economics , Economics , Forecasting , Nature , Science/economicsABSTRACT
The photochemistry of the ClO dimer (ClOOCl) plays a central role in the catalytic destruction of polar stratospheric ozone. In spite of decades of intense investigations, some of its laboratory photochemical data had not reached the desired accuracy to allow a reliable simulation of the stratospheric ozone loss until recently. Inevitable impurities in ClOOCl samples have obstructed conventional measurements. In particular, an absorption measurement of ClOOCl in 2007, which gave much lower cross sections than previous studies, implied that the formation of the ozone hole cannot be explained with current chemical models. Scientists have wondered whether the model is insufficient or the data is erroneous. Efforts aiming to resolve this controversy are reviewed in this paper, which emphasizes newly developed experiments to determine two critical photochemical properties of ClOOCl--its absorption cross section and product branching ratio--including the first reported product branching ratio at 351.8â nm photolysis.
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Photodissociation of amino acid tryptophan in a molecular beam at wavelengths of 212.8 and 193 nm, corresponding to excitation to the second and third absorption bands, was investigated using multimass ion imaging techniques. The respective wavelengths also represent excitation to the edge of a positive circular dichroism band and the center of a negative circular dichroism band of L-tryptophan. Only one dissociation channel was observed at both photolysis wavelengths: C(8)NH(6)CH(2)CHNH(2)COOH-->C(8)NH(6)CH(2)+CHNH(2)COOH. Dissociation rates were found to be 1.3x10(6) and 5x10(6) s(-1) at the respective wavelengths. Comparison to theoretical calculation indicates that dissociation occurs on the ground state after internal conversion. Implication of asymmetric photolysis is discussed.
Subject(s)
Photolysis , Tryptophan/chemistry , Electrons , Kinetics , ThermodynamicsABSTRACT
The photodissociation of benzoic acid at 193 and 248 nm was investigated using multimass ion imaging techniques. Three dissociation channels were observed at 193 nm: (1) C(6)H(5)COOH-->C(6)H(5)+COOH, (2) C(6)H(5)COOH-->C(6)H(5)CO+OH, and (3) C(6)H(5)COOH-->C(6)H(6)+CO(2). Only channels, (2) and (3), were observed at 248 nm. Comparisons of the ion intensities and photofragment translational energy distributions with the potential energies obtained from ab initio calculations and the branching ratios obtained from the Rice-Ramsperger-Kassel-Marcus theory suggest that the dissociation occurs on many electronic states.
Subject(s)
Benzoic Acid/chemistry , Quantum Theory , Photochemistry , Thermodynamics , Ultraviolet RaysABSTRACT
Multiphoton dissociation and ionization of 2,5-dihydroxyacetophenone (DHAP), an important matrix compound in UV matrix-assisted laser desorption/ionization (MALDI), is studied in a molecular beam at 355 nm using multimass ion imaging mass spectrometer and time-of-flight mass spectrometry. For laser fluence larger than 130 mJ/cm(2), nearly all of the irradiated molecules absorb at least one photon. The absorption cross section was found to be sigma = 1.3(+/-0.2) x 10(-17)cm(2). Molecules excited by two photons quickly dissociate into fragments. The major channels are (1) C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2)CO + CH(3) and (2) C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2) + COCH(3). Molecules absorbing three or more photons become parent ions or crack into smaller ionic fragments. The concentration ratio of ions (parent ions and ionic fragments) to neutral fragments is about 10(-6):1. Changing the molecular beam carrier gas from He at 250 Torr to Ar at 300 Torr results in molecular beam clustering (dimers and trimers). Multiphoton ionization of clusters by a 355 nm laser beam produces only dimer cations, (C(6)H(3)(OH)(2)COCH(3))(2)(+). Protonated clusters or negatively charged ions, observed from a solid sample of DHAP using 355 nm multiphoton ionization, were not found in the molecular beam. The experimental results indicate that the photoionization occurs in the gas phase after DHAP vaporizes from the solid phase may not play an important role in the MALDI process.
Subject(s)
Acetophenones/chemistry , Photochemical Processes , Photons , Spectrometry, Mass, Matrix-Assisted Laser Desorption-IonizationABSTRACT
Recently, discrepancies in laboratory measurements of chlorine peroxide (ClOOCl) absorption cross sections have cast doubt on the validity of current photochemical models for stratospheric ozone degradation. Whereas previous ClOOCl absorption measurements all suffered from uncertainties due to absorption by impurities, we demonstrate here a method that uses mass-selected detection to circumvent such interference. The cross sections of ClOOCl were determined at two critical wavelengths (351 and 308 nanometers). Our results are sufficient to resolve the controversial issue originating from the ClOOCl laboratory cross sections and suggest that the highest laboratory estimates for atmospheric photolysis rates of ClOOCl, which best explain the field measurements via current chemical models, are reasonable.
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The reaction of F2 + C3H6 has been investigated with the crossed molecular beam technique. The only observed primary product channel is F + C3H6F while the HF + C3H5F channel cannot be found. The reaction cross section was measured as a function of collision energy and the reaction threshold was determined to be 2.4 +/- 0.3 kcal/mol. Compared to the reaction threshold of the F2 + C2H4 reaction, the methyl substitution effectively reduces the reaction threshold by about 3 kcal/mol. The product time-of-flight spectra and angular distributions were measured and analyzed. The angular distribution displays strongly backward, indicating that the reaction is much faster than rotation. All experimental results support a rebound reaction mechanism, which agrees with the structure of the calculated transition state. The transition state geometry also suggests an early barrier; such dynamics is consistent with the observed small kinetic energy release of the products. Except for the different values of the reaction thresholds, the dynamics of the F2 + C2H4 and F2 + C3H6 reactions are remarkably similar.
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Photodissociation experiments employing molecular beams of N-methylindole, N-methylpyrrole, and anisole at 193 and 248 nm, respectively, have been conducted using multimass ion imaging techniques. We find that CH3 elimination is the sole dissociation channel for the studied molecules at both 193 and 248 nm. The photofragment translational energy distribution of anisole is found to contain both fast and slow components at the two wavelengths. On the other hand, a fast component (large recoil velocity) is dominant for N-methylindole at 248 nm, and a slow component (small recoil velocity) is dominant at 193 nm. The absorption coefficient of N-methylpyrrole is too weak for study at 248 nm. The photofragment translational energy distribution at 193 nm includes a large portion of the slow component and a small portion of the fast component. The findings indicate that the fast component corresponds to dissociation from the repulsive excited state and the slow component corresponding to dissociation from the ground electronic state. A comparison with the photodissociation dynamics of phenol, pyrrole, and indole suggests that replacement of the H atom by CH3 does not change the dissociation channels on the excited state. However, the respective dissociation channels for anisole and N-methylpyrrole on the ground state differ significantly from that for phenol and pyrrole.
Subject(s)
Anisoles/chemistry , Indoles/chemistry , Photolysis , Pyrroles/chemistryABSTRACT
The photodissociation of phenol at 193 and 248 nm was studied using multimass ion-imaging techniques and step-scan time-resolved Fourier-transform spectroscopy. The major dissociation channels at 193 nm include cleavage of the OH bond, elimination of CO, and elimination of H(2)O. Only the former two channels are observed at 248 nm. The translational energy distribution shows that H-atom elimination occurs in both the electronically excited and ground states, but elimination of CO or H(2)O occurs in the electronic ground state. Rotationally resolved emission spectra of CO (1
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Photodissociation of 3-(methylthio)propylamine and cysteamine, the chromophores of S atom containing amino acid methionine and cysteine, respectively, was studied separately in a molecular beam at 193 nm using multimass ion imaging techniques. Four dissociation channels were observed for 3-(methylthio)propylamine, including (1) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)SCH(2)CH(2)CH(2)NH+H, (2) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)+SCH(2)CH(2)CH(2)NH(2), (3) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)S+CH(2)CH(2)CH(2)NH(2), and (4) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)SCH(2)+CH(2)CH(2)NH(2). Two dissociation channels were observed from cysteamine, including (5) HSCH(2)CH(2)NH(2)-->HS+CH(2)CH(2)NH(2) and (6) HSCH(2)CH(2)NH(2)-->HSCH(2)+CH(2)NH(2). The photofragment translational energy distributions suggest that reaction (1) and parts of the reactions (2), (3), (5) occur on the repulsive excited states. However, reaction (4), (6) occur only after the internal conversion to the electronic ground state. Since the dissociation from an excited state with a repulsive potential energy surface is very fast, it would not be quenched completely even in the condensed phase. Our results indicate that reactions following dissociation may play an important role in the UV photochemistry of S atom containing amino acid chromophores in the condensed phase. A comparison with the potential energy surface from ab initio calculations and branching ratios from RRKM calculations was made.
Subject(s)
Amino Acids/chemistry , Chemistry, Physical/methods , Photochemistry/methods , Sulfur/chemistry , Cysteine/chemistry , Electrons , Hydrogen , Ions , Methionine/chemistry , Models, Chemical , Molecular Conformation , Molecular Structure , Propylamines/chemistry , Ultraviolet RaysABSTRACT
The photodissociation of p-methylphenol, p-ethylphenol, and p-(2-aminoethyl)phenol, chromophores of the amino acid tyrosine, was studied separately for each compound in a molecular beam at 248 nm using multimass ion imaging techniques. They show interesting side-chain size-dependent dissociation properties. Only one dissociation channel, that is, H atom elimination, was observed for both p-methylphenol and p-ethylphenol. The photofragment translational energy distributions and potential energy surfaces from ab initio calculation suggest that H atom elimination occurs from a repulsive excited state. On the other hand, the H atom elimination channel is quenched completely by internal conversion and/or intersystem crossing in p-(2-aminoethyl)phenol. Only C-C bond cleavage was observed from p-(2-aminoethyl)phenol. The photofragment translational energy distribution shows a slow component and a fast component. The fast component results from dissociation on an electronic excited state, but the slow component occurs only after the internal conversion to the ground electronic state. Comparison with the photodissociation of phenol and ethylbenzene is made.
Subject(s)
Phenols/chemistry , Tyramine/chemistry , Tyrosine/chemistry , Computer Simulation , Models, Molecular , Molecular Structure , PhotochemistryABSTRACT
Photodissociation of nitrobenzene at 193, 248, and 266 nm and o-nitrotoluene at 193 and 248 nm was investigated separately using multimass ion imaging techniques. Fragments corresponding to NO and NO(2) elimination from both nitrobenzene and o-nitrotoluene were observed. The translational energy distributions for the NO elimination channel show bimodal distributions, indicating two dissociation mechanisms involved in the dissociation process. The branching ratios between NO and NO(2) elimination channels were determined to be NONO(2)=0.32+/-0.12 (193 nm), 0.26+/-0.12 (248 nm), and 0.4+/-0.12(266 nm) for nitrobenzene and 0.42+/-0.12(193 nm) and 0.3+/-0.12 (248 nm) for o-nitrotoluene. Additional dissociation channels, O atom elimination from nitrobenzene, and OH elimination from o-nitrotoluene, were observed. New dissociation mechanisms were proposed, and the results are compared with potential energy surfaces obtained from ab initio calculations. Observed absorption bands of photodissociation are assigned by the assistance of the ab initio calculations for the relative energies of the triplet excited states and the vertical excitation energies of the singlet and triplet excited states of nitrobenzene and o-nitrotoluene. Finally, the dissociation rates and lifetimes of photodissociation of nitrobenzene and o-nitrotoluene were predicted and compared to experimental results.