ABSTRACT
Geometric phase (GP) effects in chemical reactions are subtle quantum phenomena that are challenging to identify. In this work, we report a joint experimental and theoretical study of the H + HD â H2 + D reaction at a collision energy of 2.07 eV, which is far below the energy of the conical intersection of 2.53 eV. The rotationally state-resolved differential cross sections were measured by a crossed-beam experiment with the scheme of D-atom Rydberg tagging time-of-flight detection. Experimental angular distributions of three rotational states of H2 products exhibit notable variation near the backward scattering direction. Time-dependent quantum mechanics calculations (TDQMs) were carried out at the same collision energy, with and without the inclusion of GP. The experimental angular distributions are in good agreement with TDQM results with the inclusion of GP but do not agree with TDQM results without the inclusion of GP. This work demonstrates the existence of GP effects at energy far below the conical intersection.
ABSTRACT
The vibrationally excited reaction O(1D) + CHD3(ν1 = 1) has been investigated by crossed-molecular-beam experiments with a time-sliced velocity map imaging technique. Detailed and quantitative information is extracted on the C-H stretching excitation effects on the reactivity and dynamics of the title reaction, with the help of preparation of C-H stretching excited CHD3 molecules by direct infrared excitation. Experimental results show that the vibrational stretching excitation of the C-H bond almost does not affect the relative contributions between different dynamical pathways for all product channels. For the OH + CD3 product channel, the vibrational energy of the C-H stretching excited CHD3 reagent is channeled exclusively into the vibrational energy of the OH products. The vibrational excitation of the CHD3 reactant changes the reactivities for the ground-state and umbrella-mode-excited CD3 channels very modestly, while it significantly suppresses the corresponding CHD2 channels. For the CHD2(ν1 = 1) channel, the stretching excited C-H bond of the CHD3 molecule acts almost as a pure spectator.
ABSTRACT
Structural characterization of neutral water clusters is crucial to understanding the structures and properties of water, but it has been proven to be a challenging experimental target due to the difficulty in size selection. Here, we report the size-specific infrared spectra of confinement-free neutral water nonamer (H2O)9 based on threshold photoionization, using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals in the 3200-3350 cm-1 region are observed, providing unique spectral signatures for the formation of an unprecedented (H2O)9 structure evolved by adding a ninth water molecule onto a hydrogen bond-unbroken edge of the (H2O)8 octamer with D2d symmetry. This nonamer structure coexists with the five previously identified structures that can be viewed as derived by inserting a ninth water molecule into a hydrogen bond-broken edge of the D2d/S4 octamer. These findings provide key microscopic information for systematic understanding of the formation and growth mechanism of dynamical hydrogen-bonding networks that are responsible for the structure and properties of condensed-phase water.
ABSTRACT
State-to-state photodissociation of CO2(v2 = 0 and 1) at 157 nm via the O(1D) + CO(X1Σ+) channel was studied by using the sliced velocity map imaging technique. Both the O(1D) and CO(X1Σ+) products were detected by (2 + 1) resonance enhanced multiphoton ionization (REMPI). Detection of CO via the B1Σ+ ââ X1Σ+ transition allowed ro-vibrational state-selective detection, and combined with imaging, the fragment energy and angular distributions have been derived. For CO(v = 0 and 1|j) products from the CO2(v2 = 0) molecule, the angular distributions of low-j CO display positive anisotropic parameters (about 0.8); with j increasing, the product anisotropic parameters gradually reduce to zero. While for CO(v = 0 and 1|j) products from the vibrational excited CO2(v2 = 1) molecule, the angular distributions of low-j CO also display positive anisotropic parameters; with j increasing, the product anisotropic parameters first decrease to zero and then become negative (about -0.5). Experimental results show that the observed variation of the product angular distribution with the rotational quantum number of CO is consistent with trends predicted by a classical model for non-axial fragment recoil. The results support advanced theoretical predictions of a predominantly parallel transition to the bent 21A' excited state of CO2, where bending introduces torque during the direct dissociation process.
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Band structure dictates optical and electronic properties of solids and eventually the efficiency of the semiconductor based solar conversion. Compared to numerous theoretical calculations, the experimentally measured band structure of rutile TiO2, a prototypical photocatalytic material, is rare. In this work, the valence band structure of rutile TiO2(110) is measured by angle-resolved photoelectron spectroscopy using polarized extreme ultraviolet light. The effective mass of the hole, which has never been measured before, is determined to be 4.66-6.87 m0 (free electron mass) and anisotropic. The dependence of photoemission intensities on excitation light polarization is analyzed by taking into account of the parity symmetry of molecular orbitals in the blocking unit of rutile TiO2. This work reports a direct measurement of valence band structure and hole effective mass of rutile TiO2(110), which will deepen our understanding of the electronic structure and charge carrier properties of the model material and provide reference data for future theoretical calculations.
ABSTRACT
A neutral boron carbonyl complex B4 (CO)3 is generated in the gas phase and is characterized by infrared plus vacuum ultraviolet (IR+VUV) two-color ionization spectroscopy and quantum chemical calculations. The complex is identified to have a planar C2v structure with three CO ligands terminally coordinated to a rhombus B4 core. It has a closed-shell singlet ground state that correlates to an excited state of B4 . Bonding analyses on B4 (CO)3 as well as the previously reported B4 and B4 (CO)2 indicate that the electronic structure of rhombus tetraboron cluster changes from a close-shell singlet to an open-shell singlet in B4 (CO)2 and to a close-shell singlet in B4 (CO)3 , demonstrating that the electronic structures of boron clusters can be effectively tuned via sequential CO ligand coordination.
ABSTRACT
The band gap state of TiO2, which is dominated by Ti3+ 3d character, is of great relevance to light absorption, electron trapping, charge recombination, and conduction band structure. Despite the importance, the explanation of the excitation from this state is controversial. To this end, the electronic structures of TiO2(110) and TiO2(011)-(2 × 1) have been systematically measured with two-photon photoemission spectroscopy. The results reveal the anisotropic nature of the electronic structure in rutile TiO2 at seemingly equivalent directions of [110] and [11Ì 0], the long axes of the TiO6 blocking unit. Although the resonant energy of these two d-d transitions is identical, the energy levels are systematically shifted by 0.1 eV. We propose this anisotropy originates from the broken symmetry of the rutile TiO2 crystals caused by the surface. The proposed asymmetry-caused electronic structure anisotropy could be generalized to other similar materials and may affect associated catalytic properties. This work provides an important benchmark for related calculations.
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Neutral titanium-metal carbonyl complexes with the chemical formula Ti(CO)n (n = 4-7) are produced in the gas phase by the reactions of titanium atoms with carbon monoxide in a pulsed laser vaporization-supersonic expansion source. Their infrared absorption spectra in the carbonyl stretching frequency region are measured by infrared plus vacuum ultraviolet (IR+VUV) two-color ionization spectroscopy based on a tunable VUV free electron laser. Infrared spectroscopy in conjunction with quantum chemical calculations confirm that all of these complexes have unexpected titanium ketenylidene OTiCCO(CO)n-2 structures. Bonding analysis indicates that the OTiCCO core structure can be described by the bonding interactions between a TiO+ cation in the doublet ground state and a doublet ground state of CCO-. The results reveal that the C-O bond breaking and C-C bond formation proceed efficiently in the reactions between laser-vaporized titanium atoms and carbon monoxide.
ABSTRACT
The water octamer with its cubic structure consisting of six four-membered rings presents an excellent cluster system for unraveling the cooperative interactions driven by subtle changes in the hydrogen-bonding topology. Despite prediction of many distinct structures, it has not been possible to extract the structural information encoded in their vibrational spectra because this requires size-selectivity of the neutral clusters with sufficient resolution to identify the contributions of the different isomeric forms. Here we report the size-specific infrared spectra of the isolated cold, neutral water octamer using a scheme based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. A plethora of sharp vibrational bands features are observed. Theoretical analysis of these patterns reveals the coexistence of five cubic isomers, including two with chirality. The relative energies of these structures are found to reflect topology-dependent, delocalized multi-center hydrogen-bonding interactions. These results demonstrate that even with a common structural motif, the degree of cooperativity among the hydrogen-bonding network creates a hierarchy of distinct species. The implications of these results on possible metastable forms of ice are speculated.
ABSTRACT
Infrared spectroscopic study of neutral water clusters is crucial to understanding of the hydrogen-bonding networks in liquid water and ice. Here we report infrared spectra of size-selected neutral water clusters, (H2O) n (n = 3-6), in the OH stretching vibration region, based on threshold photoionization using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals observed in the 3,500-3,600-cm-1 region of (H2O)5 provide unique spectral signatures for the formation of a noncyclic pentamer, which coexists with the global-minimum cyclic structure previously identified in the gas phase. The main features of infrared spectra of the pentamer and hexamer, (H2O) n (n = 5 and 6), span the entire OH stretching band of liquid water, suggesting that they start to exhibit the richness and diversity of hydrogen-bonding networks in bulk water.
ABSTRACT
We have built a high-energy, narrow-bandwidth, nanosecond light source for efficient preparation of vibrationally excited molecules in a molecular beam. It consists of an injection-seeded optical parametric oscillator and two optical parametric amplifiers. Pumped by the second harmonic of a commercial injection-seeded Nd:YAG laser, it can generate pulse energies up to 377 mJ at 655 nm with a bandwidth smaller than 200 MHz. Its stability is excellent, with a standard deviation of pulse energy of 5.2 mJ and a wavelength stability of 0.001 cm-1. We demonstrated this light source in a crossed-molecular-beam experiment of the H + D2 (v = 2, j = 0) â HD + D reaction, in which it was used for overtone excitation of D2 molecules from (v = 0, j = 0) to (v = 2, j = 0) with an overall excitation efficiency of 2.5%.
ABSTRACT
This paper describes an experimental technique for studying neutral metal complexes using infrared + vacuum ultraviolet (IR+VUV) two-color ionization spectroscopy based on a tunable VUV free-electron laser (VUV-FEL). The preliminary IR spectroscopy results of mass-selected nickel tetracarbonyl are reported in this work. The results demonstrate that the tunable VUV-FEL light allows the selective ionization of a given neutral cluster free of confinement along with the recording of well-resolved IR spectra. As the ionization energies of many neutral clusters are accessible by a broadly tunable VUV-FEL (50-150 nm) and near-threshold ionization can be readily achieved, the proposed experimental method offers unique possibilities for the size-specific study of a wide variety of confinement-free neutral clusters.
ABSTRACT
It has long been predicted that oscillatory behavior exists in reactivity as a function of collision energy for heavy-light-heavy (HLH) chemical reactions in which a light atom is transferred between two heavy atoms or groups of atoms, but direct observation of such a behavior in bimolecular reactions remains a challenge. Here we report a joint theoretical and crossed-molecular-beam study on the Cl + CH4 â HCl + CH3 reaction. A distinctive peak at a collision energy of 0.15 eV for the CH3(v = 0) product was experimentally detected in the backward scattering direction. Detailed quantum-dynamics calculations on a highly accurate potential energy surface revealed that this feature originates from the reactivity oscillation in this HLH polyatomic reaction. We anticipate that such reactivity oscillations exist in many HLH reactions involving polyatomic reagents.
ABSTRACT
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.
ABSTRACT
Infrared (IR) spectroscopy provides detailed structural and dynamical information on clusters at the fingerprint level. Herein, we demonstrate the capability of a tunable vacuum ultraviolet free electron laser (VUV-FEL) for selective detection of a wide variety of neutral water clusters and for recording the size-dependent IR spectra. The present technique does not require the presence of an ultraviolet chromophore or a dipole moment and is generally applicable for IR spectroscopy of neutral clusters free from confinement. To show the features of our technique, we report here the IR spectra of neutral water dimer in the OH stretch region, providing benchmarks for theoretical study of the accurate description of hydrogen bonding structures involved in liquid water and ice. Quantum mechanical calculations on a 12-dimensional ab initio potential energy surface are utilized to simulate the anharmonic vibrational spectra of water dimer. These results help to resolve the controversy of the exact vibrational assignment of each band feature of the water dimer.
ABSTRACT
Vibrationally excited reaction of Cl + D2 (v = 1, j = 0) â DCl + D was investigated by a high-resolution crossed beam experiment, with D2 molecules in the vibrationally excited state prepared by the scheme of stimulated Raman pumping. Differential cross sections (DCSs) were obtained at three collision energies of 4.03, 4.93, and 5.68 kcal/mol. Backward scattering is dominant for both DCl (v' = 0) and DCl (v' = 1) products, and no forward scattering signal was observed at these three collision energies. Collision-energy-dependent DCS in the backward scattering direction was measured at collision energies between 3.62 and 5.97 kcal/mol. Comparing with the DCSs from the vibrational ground state, it is found that the vibrational excitation of D2 molecules significantly enhances the reactivity because of the later barrier nature of the reaction. No obvious oscillatory structure was found in the collision-energy-dependent DCS in the backward scattering direction, suggesting that the title reaction proceeds via a direct abstraction mechanism.
ABSTRACT
According to the fishery resources investigation data in the east of the Nanji Islands during autumn in 2017 and spring in 2018, the inter-specific relationships and ecological relationships between major nekton were analyzed via the index of relative importance, niche breadth, cluster analysis, niche overlap, χ2-test, variance ratio test, association coefficient, percentage of co-occurrence, and point correlation coefficients. The results showed that there were 30 major nekton species in this area. The dominant species were Harpadon nehereus, Portunus trituberculatus, and Oratosquilla oratoria. The niche width of these dominant species was relatively wide. Based on the cluster analysis of niche breadth, the 30 major nekton species could be divided into three categories, wide niche breadth species, moderate niche breath species, and narrow niche breath species. The distribution range of niche overlap value was [0, 0.98], indicating that there were differences in the similarity of species to resource utilization and that the niche was differentiated and accompanied by inter-specific competition. The values of VR and W showed that there was a significant positive correlation among the major nekton species. The χ2-test results indicated significantly interspecific association for 76 species pair (χ2≥3.841), which was related to community stability and species coexistence. Results of association coefficient, percentage of co-occurrence and point correlation coefficients test suggested that the interspecific association was strong and tended to be positive.
Subject(s)
Ecosystem , Fisheries , Animals , Fishes , Islands , SeasonsABSTRACT
The ultrafast decay dynamics of water molecules excited to D[combining tilde]'1B1 and D[combining tilde]''1A2 states is studied by combining two-photon excitation and time-resolved photoelectron imaging methods. The lifetime of the D[combining tilde]'1B1(000) state of H2O (D2O) is determined to be 1.54 ± 0.1 (22.6 ± 1.6) ps, consistent with a previous high-resolution spectroscopic study. The H2O D[combining tilde]''1A2(000) state decays with a lifetime of 4.1 ± 0.2 ps, while in the D2O D[combining tilde]''1A2(000) state, two independent decay pathways are observed, with time constants of 0.55 ± 0.1 and 13 ± 1 ps, respectively. The former is proposed to be associated with a hitherto undocumented D[combining tilde]'' â C[combining tilde] pathway, induced by Coriolis interaction.
ABSTRACT
Chemical reactions are important in the evolution of low-temperature interstellar clouds, where the quantum tunnelling effect becomes significant. The F + para-H2 â HF + H reaction, which has a significant barrier of 1.8 kcal mol-1, is an important source of HF in interstellar clouds; however, the dynamics of this quantum-tunnelling-induced reactivity at low temperature is unknown. Here, we show that this quantum tunnelling is caused by a post-barrier resonance state. Quantum-state-resolved crossed-beam scattering measurements reveal that this resonance state has a collision energy of ~5 meV and a lifetime of ~80 fs, which are in excellent agreement with a recent anion photoelectron spectroscopic study. Accurate quantum reactive scattering calculations on the new iCSZ-LWAL potential energy surfaces provides a detailed explanation of the experimental results. The reaction rate for this system was also theoretically determined accurately at temperatures as low as 1 K.
ABSTRACT
We report a real-space imaging of formaldehyde (HCHO) adsorption on a TiO2(110) surface probed by high-resolution scanning tunnelling microscopy (STM). Density functional theory calculations (DFT) were carried out to assign the observed features. The adsorptions occur exclusively on 5-fold coordinated Ti (Ti5c) sites and oxygen vacancies (OVs). The well-resolved configurations on the Ti5c sites feature the overlapping of the two "dumbbell" structures which are originated from the empty orbitals of HCHO. The STM images for the physical adsorption of HCHO on the OV sites appear fuzzy because of the rapid switching of HCHO among the three stable orientations, while those for the chemical adsorption are much clearer, revealing a distinctive difference between chemical and physical adsorptions. This work presents a systematic characterization of the topological features of HCHO/TiO2(110) and provides useful information for mechanical understanding of the reaction mechanism of HCHO on the surfaces.