Resonance-enhanced Multiphoton Ionization Technique Research Articles

N-H and N-C Bond Dissociation Pathways in Ultraviolet Photodissociation of Dimethylamine.

We investigated the interlinked N-H and N-C photochemistry of primary and secondary amines via the state-resolved detection of vibrationally excited CH3 product and H atom product by 200-235 nm dimethylamine photodissociation using resonance-enhanced multiphoton ionization (REMPI) and velocity map imaging (VMI) techniques. The out-of-plane bending (ν2) vibrationally excited CH3 showed a bimodal translational energy distribution that became unimodal with a near-zero product yield at longer photolysis wavelengths (λphotolysis). In contrast, a unimodal distribution was observed for the C-H stretching (νCH) vibrationally excited CH3 products with an almost constant product yield in the examined λphotolysis region. We ascribed the state-specific energy releases of the CH3 products to two reaction pathways based on calculations of the potential energy surface (PES): the direct N-CH3 dissociation pathway and the indirect N-CH3 dissociation pathway via the N-H bond conical intersection. Meanwhile, the H atom product showed a bimodal energy distribution similar to the ammonia photodissociation model, with an excited-state counterproduct channel that became accessible at a shorter λphotolysis. These results suggest that the N-H and N-C bond dissociations are connected, and these dissociations cause different photochemistry between primary/secondary amines and tertiary amines.

New light on the use of Theobroma cacao by Late Classic Maya

Cacao seeds, Theobroma cacao, provide the basis for a ceremonially important Mesoamerican food. Past efforts to identify cacao in ceramics focused on highly decorative vessel forms associated with elite ceremonial contexts, creating assumptions as to how cacao was distributed and who could access it. This study examines 54 archaeological ceramic sherds from El Pilar (Belize/Guatemala) of Late Classic (600 to 900 CE) residential and civic contexts representing a cross-section of ancient Maya inhabitants. Identification of cacao in ancient sherds has depended on the general presence of theobromine; we used the discrete presence of theophylline, a unique key biomarker for cacao in the region. Analysis was done by grinding off all outside surfaces to reduce contamination, pulverizing the inner clay matrix, extracting absorbed molecules, and concentrating the extractions. In order to obtain especially high selectivity and low limits of detection, our study utilized the technique of resonance-enhanced multiphoton ionization coupled with laser-desorption jet-cooling mass spectrometry. This technique isolates molecules in the cold gas phase where they can be selectively ionized through a resonant two-photon process. Of the sherds analyzed, 30 samples (56%) were found to contain significant amounts of theophylline and thus test positive for cacao. Importantly, cacao is present in all contexts, common to all Maya residents near and far from centers.

Photodissociation Dynamics of Vinoxy Radical via the B̃2A″ State: The H + CH2CO Product Channel.

Photodissociation dynamics of the jet-cooled vinoxy radical (CH2CHO) via the B̃2A″ state was studied in the near-ultraviolet (near-UV) region of 308-328 nm using high-n Rydberg H atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The vinoxy radical beam was produced by 193 nm photolysis of ethyl vinyl ether followed by supersonic expansion. The H + CH2CO product channel was observed directly in the H atom TOF spectra. The H atom photofragment yield (PFY) spectra were obtained by integrating the H atom TOF spectra and measuring the H atom REMPI signals, and showed several vibronic bands of the B̃2A″ state. The translational energy distributions of the H + CH2CO products, P(ET)'s, were obtained at several vibronic transitions. The P(ET) distributions were broad, peaking at a low energy of ∼3500 cm-1. The product translational energy release was moderate; the average translational energy release in the maximum available energy, ⟨fT⟩, was in the range of 0.24-0.27. The product angular distributions in this wavelength region were slightly anisotropic, with the β parameter in the range of 0.10-0.24. The near-UV photodissociation mechanism of the H + CH2CO product channel of the vinoxy radical is consistent with unimolecular dissociation on the electronic ground state (X̃2A″) following internal conversion from the B̃2A″ state to the Ã2A' state and then to the X̃2A″ state (although unimolecular dissociation from the first excited Ã2A' may also contribute).

Photostimulated desorption of OH radicals from amorphous solid water: Evidence for the interaction of visible light with an OH-ice complex

Using a combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques, OH radicals photodesorbed from amorphous solid water at low temperatures are detected. It was found that the OH photodesorption can be caused by a one-photon process on the surface even at 532 nm, where both isolated OH and ${\mathrm{H}}_{2}\mathrm{O}$ are transparent. Quantum chemical calculations reveal that the electronic excitation of OH dramatically changes depending on the adsorption sites and the number of surrounding ${\mathrm{H}}_{2}\mathrm{O}$ molecules, and that OH having three hydrogen bonds with neighboring ${\mathrm{H}}_{2}\mathrm{O}$ molecules can absorb photons of around 532 nm, which supports the experimental findings.

Direct measurement of fast ortho-para conversion of molecularly chemisorbed H2 on Pd(210)

Ortho-para conversion of molecularly chemisorbed ${\mathrm{H}}_{2}$ on a Pd(210) surface at a surface temperature of 50 K is reported. A combination of a pulsed molecular beam, photostimulated desorption, and resonance-enhanced multiphoton ionization techniques was used for probing the change in the rotational states of molecularly chemisorbed ${\mathrm{H}}_{2}$ on the surface. Our result shows that fast ortho-para conversion of chemisorbed ${\mathrm{H}}_{2}$ occurs. The conversion time was experimentally determined to be about 2 s, which is in good agreement with a previous theoretical calculation. This agreement supports that the ortho-para conversion mechanism of the molecularly chemisorbed ${\mathrm{H}}_{2}$ on Pd(210) is a two-step process based on the hyperfine-Coulomb excitation.

Characterization of Si atomic transitions using pulsed electric discharge and resonance-enhanced multiphoton ionization techniques

A pulsed high-voltage electric discharge jet coupled with mass-selective REMPI was used to characterize Si atomic transitions with increased sensitivity.

Surface Temperature Dependence of Hydrogen Ortho-Para Conversion on Amorphous Solid Water.

The surface temperature dependence of the ortho-to-para conversion of H_{2} on amorphous solid water is first reported. A combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques allowed us to sensitively probe the conversion on the surface of amorphous solid water at temperatures of 9.2-16K. Within a narrow temperature window of 8K, the conversion time steeply varied from ∼4.1×10^{3} to ∼6.4×10^{2} s. The observed temperature dependence is discussed in the context of previously suggested models and the energy dissipation process. The two-phonon process most likely dominates the conversion rate at low temperatures.

Ultraviolet Photodissociation Dynamics of the Allyl Radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) Electronic Excited States.

Ultraviolet (UV) photodissociation dynamics of jet-cooled allyl radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) electronically excited states are studied at the photolysis wavelengths from 249 to 216 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The photofragment yield (PFY) spectra of the H atom products are measured using both allyl chloride and 1,5-hexadiene as precursors of the allyl radical and show a broad peak centered near 228 nm, whereas the previous UV absorption spectra of the allyl radical peak around 222 nm. This difference suggests that, in addition to the H + C3H4 product channel, another dissociation channel (likely CH3 + C2H2) becomes significant with increasing excitation energy. The product translational energy release of the H + C3H4 products is modest, with the P(ET) distributions peaking near 8.5 kcal/mol and the fraction of the average translational energy in the total excess energy, ⟨fT⟩, in the range 0.22-0.18 from 249 to 216 nm. The P(ET)'s are consistent with production of H + allene and H + propyne, as suggested by previous experimental and theoretical studies. The angular distributions of the H atom products are isotropic, with the anisotropy parameter β ≈ 0. The H atom dissociation rate constant from the pump-probe study gives a lower limit of 1 × 10(8)/s. The dissociation mechanism is consistent with unimolecular decomposition of the hot allyl radical on the ground electronic state after internal conversion of the electronically excited state.

The design of double electrostatic-lens optics for resonance enhanced multiphoton ionization and photoelectron imaging experiments.

Compared to single ion/electron-optics for velocity-map imaging, a double-focusing lens assembly designed not only allows for mapping velocity imaging of photoelectrons but also allows for investigating the vibrational structure of the intermediate states of neutral species in resonance enhanced multiphoton ionization (REMPI) spectra. In this presentation, in order to record REMPI and photoelectron spectra separately, we have constructed a compact photoelectron velocity-map imaging (VMI) apparatus combined with an opposite linear Wiley-Mclaren time-of-flight mass spectrometer (TOFMS). A mass resolution (m/Δm) of ∼1300 for TOFMS and electron energy resolution (ΔE/E) of 2.4% for VMI have been achieved upon three-photon ionization of Xe atom at 258.00 nm laser wavelength. As a benchmark, in combination of one-color (1 + 1) REMPI and photoelectron imaging of benzene via 6(1) and 6(1)1(1) vibronic levels in the S1 state, the vibrational structures of the cation and photoelectron angular anisotropy are unraveled. In addition, two-color (1 + 1') REMPI and photoelectron imaging of aniline was used to complete the accurate measurement of ionization potential (62,271 ± 3 cm(-1)). The results suggest that the apparatus is a powerful tool for studying photoionization dynamics in the photoelectron imaging using vibrational-state selected excitation to the intermediate states of neutrals based on REMPI technique.

Photodissociation Dynamics of Benzoyl Chloride at 235 nm: Resonance-Enhanced Multiphoton Ionization Detection of Cl and HCl

The photodissociation dynamics of benzoyl chloride at 235 nm has been investigated and compared with that of 2-furoyl chloride. Atomic Cl and molecular HCl channels have been detected in benzoyl chloride by employing resonance-enhanced multiphoton ionization technique and time-of-flight mass spectrometry. Both the Cl fragments, Cl((2)PJ=3/2, relative quantum yield 0.70 ± 0.15) and Cl*((2)PJ=1/2), show isotropic angular distribution and bimodal translational energy distributions. The predominant high kinetic energy channel contributes 72% to the C-Cl bond scission and arises from the S1 state having nπ* character of benzoyl chloride. However, the low-energy Cl and HCl channels originate from the ground electronic state. The most plausible mechanism of HCl formation is proposed based on molecular orbital calculations. In contrast to benzoyl chloride, the HCl channel is not observed in 2-furoyl chloride on excitation at 235 nm, and this is attributed to an energy constraint.

Rotational spectroscopy with an optical centrifuge

We demonstrate a new spectroscopic method for studying electronic transitions in molecules with extremely broad range of angular momentum. We employ an optical centrifuge to create narrow rotational wave packets in the ground electronic state of (16)O2. Using the technique of resonance-enhanced multi-photon ionization, we record the spectrum of multiple ro-vibrational transitions between X(3)Σg(-) and C(3)Πg electronic manifolds of oxygen. Direct control of rotational excitation, extending to rotational quantum numbers as high as N ≳ 120, enables us to interpret the complex structure of rotational spectra of C(3)Πg beyond thermally accessible levels.

The Application of Resonance-Enhanced Multiphoton Ionization Technique in Gas Chromatography Mass Spectrometry

Gas chromatography resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (GC/REMPI-TOFMS) using a nanosecond laser has been applied to analyze the 16 polycyclic aromatic hydrocarbons (PAHs). The excited-state lifetime, absorption characters, and energy of electronic states of the 16 PAHs were investigated to optimize the ionization yield. A river water sample pretreated by means of solid phase extraction was analyzed to evaluate the performance of the analytical instrument. The results suggested that REMPI is superior to electron impact ionization method for soft ionization and suppresses the background signal due to aliphatic hydrocarbons. Thus, GC/REMPI-TOFMS is a more reliable method for the determination of PAHs present in the environment.

Spatially resolved measurement of singlet delta oxygen by radar resonance-enhanced multiphoton ionization

Coherent microwave Rayleigh scattering (Radar) from resonance-enhanced multiphoton ionization (REMPI) was demonstrated to directly and nonintrusively measure singlet delta oxygen, O(2)(a(1)Δ(g)), with high spatial resolution. Two different approaches, photodissociation of ozone and microwave discharge plasma in an argon and oxygen flow, were utilized for O(2)(a(1)Δ(g)) generation. The d(1)Π(g)←a(1)Δ(g) (3-0) and d(1)Π(g)←a(1)Δ(g) (1-0) bands of O(2)(a(1)Δ(g)) were detected by Radar REMPI for two different flow conditions. Quantitative absorption measurements using sensitive off-axis integrated cavity output spectroscopy (ICOS) was used simultaneously to evaluate the accuracy and sensitivity of the Radar REMPI technique. The detection limit of Radar REMPI was found to be comparable to the ICOS technique with a detection threshold of approximately 10(14) molecules/cm(3) but with a spatial resolution that was 8 orders of magnitude smaller than the ICOS technique.

Competitive Bond Rupture in the Photodissociation of Bromoacetyl Chloride and 2- and 3-Bromopropionyl Chloride: Adiabatic versus Diabatic Dissociation

Competitive bond dissociation mechanisms for bromoacetyl chloride and 2- and 3-bromopropionyl chloride following the (1) [n(O)→π*(C=O)] transition at 234-235 nm are investigated. Branching ratios for C−Br/C−Cl bond fission are found by using the (2+1) resonance-enhanced multiphoton ionization (REMPI) technique coupled with velocity ion imaging. The fragment branching ratios depend mainly on the dissociation pathways and the distances between the orbitals of Br and the C=O chromophore. C−Cl bond fission is anticipated to follow an adiabatic potential surface for a strong diabatic coupling between the n(O)π*(C=O) and np (Cl)σ*(C−Cl) bands. In contrast, C−Br bond fission is subject to much weaker coupling between n(O)π*(C=O) and np (Br)σ*(C−Br). Thus, a diabatic pathway is preferred for bromoacetyl chloride and 2-bromopropionyl chloride, which leads to excited-state products. For 3-bromopropionyl chloride, the available energy is not high enough to reach the excited-state products such that C−Br bond fission must proceed through an adiabatic pathway with severe suppression by nonadiabatic coupling. The fragment translational energies and anisotropy parameters for the three molecules are also analyzed and appropriately interpreted.

Directional spinning of molecules with sequences of femtosecond pulses

We present an analysis of two experimental approaches to controlling the directionality of molecular rotation with ultrashort laser pulses. The two methods are based on the molecular interaction with either a pair of pulses (a ``double-kick'' scheme) or a longer pulse sequence (a ``chiral-pulse-train'' scheme). In both cases, rotational control is achieved by varying the polarization of and the time delay between the consecutive laser pulses. Using the technique of polarization-sensitive resonance-enhanced multiphoton ionization, we show that both methods produce significant rotational directionality. We demonstrate that increasing the number of excitation pulses supplements the ability to control the sense of molecular rotation with quantum-state selectivity, i.e., predominant excitation of a single rotational state. We also demonstrate the ability of both techniques to generate counterrotation of molecular nuclear-spin isomers (here, ortho- and para-nitrogen) and molecular isotopologs (here, ${}^{14}$N${}_{2}$ and ${}^{15}$N${}_{2}$).

Dynamics of C[sbnd]Cl bond fission in photodissociation of 2-furoyl chloride at 235 nm

The photodissociation dynamics of 2-furoyl chloride at 235nm has been investigated, employing resonance-enhanced multiphoton ionization technique and time-of-flight mass spectrometry. Both the Cl fragments, Cl(2PJ=3/2, relative quantum yield 0.85±0.11) and Cl∗(2PJ=1/2), have the recoil anisotropy parameter (β) value close to zero, and show bimodal translational energy distributions. The branching ratio of the high kinetic energy CCl bond scission to the low energy CCl scission is 0.78/0.22. The dominant high kinetic energy channel arises mainly because of electronic pre-dissociation. But, the low energy channel results from the ground electronic state of 2-furoyl chloride, formed subsequent to non-radiative relaxation of the initially prepared excited state.

Direct measurement of methyl radicals in a methane/air flame at atmospheric pressure by radar REMPI

We report the direct measurements of methyl radicals (CH(3)) in methane/air flames at atmospheric pressure by using coherent microwave Rayleigh scattering (Radar) from Resonance Enhanced Multi-Photon Ionization (REMPI), also known as the Radar REMPI technique. A tunable dye laser was used to selectively induce the (2 + 1) REMPI ionization of methyl radicals (CH(3), 3p(2)A(2)('')0(0)(0) band) in a near adiabatic and premixed laminar methane/air flame, generated by a Hencken burner. In situ measurements of the REMPI electrons were made by non-intrusively using a microwave homodyne transceiver detection system. The REMPI spectrum of the CH(3) radical was obtained and a spatial distribution of the radicals limited by focused laser beam geometry, approximately 20 µm normal to the flame front and 2.4 mm parallel to the flame, was determined. The measured CH(3) was in good agreement with numerical simulations performed using the detailed kinetic mechanism of GRI-3.0. To the authors' knowledge, these experiments represent the first directly-measured spatially-resolved CH(3) in a flame at atmospheric pressure.

A theoretical and experimental study on translational and internal energies of H2O and OH from the 157 nm irradiation of amorphous solid water at 90 K

The photodesorption of H(2)O in its vibrational ground state, and of OH radicals in their ground and first excited vibrational states, following 157 nm photoexcitation of amorphous solid water has been studied using molecular dynamics simulations and detected experimentally by resonance-enhanced multiphoton ionization techniques. There is good agreement between the simulated and measured energy distributions. In addition, signals of H(+) and OH(+) were detected in the experiments. These are inferred to originate from vibrationally excited H(2)O molecules that are ejected from the surface by two distinct mechanisms: a direct desorption mechanism and desorption induced by secondary recombination of photoproducts at the ice surface. This is the first reported experimental evidence of photodesorption of vibrationally excited H(2)O molecules from water ice.

Molecular elimination of methyl formate in photolysis at 234 nm: roaming vs. transition state-type mechanism

Ion imaging coupled with (2 + 1) resonance-enhanced multiphoton ionization (REMPI) technique is employed to probe CO(v″ = 0) fragments at different rotational levels following photodissociation of methyl formate (HCOOCH(3)) at 234 nm. When the rotational level, J″(CO), is larger than 24, only a broad translational energy distribution extending beyond 70 kcal mol(-1) with an average energy of about 23 kcal mol(-1) appears. The dissociation process is initiated on the energetic ground state HCOOCH(3) that surpasses a tight transition state along the reaction coordinate prior to breaking into CO + CH(3)OH. This molecular dissociation pathway accounts for the CO fragment with larger rotational energy and large translational energy. As J″(CO) decreases, a bimodal distribution arises with one broad component and the other sharp component carrying the average energy of only 1-2 kcal mol(-1). The branching ratio of the sharp component increases with a decrease of J″(CO); (7.3 ± 0.6)% is reached as the image is probed at J″(CO) = 10. The production of a sharp component is ascribed to a roaming mechanism that has the following features: a small total translational energy, a low rotational energy partitioning in CO, but a large internal energy in the CH(3)OH co-product. The internal energy deposition in the fragments shows distinct difference from those via the conventional transition state.

Translational and rotational energy measurements of desorbed water molecules in their vibrational ground state following 157 nm irradiation of amorphous solid water

Water ice is the major solid component in a variety of astrophysical environments, e.g., cold and dense molecular clouds. Photodesorption plays a dominant role in consuming ice in such cold regions. In this study, photodesorption of vibrationally ground-state H 2O( v = 0) from amorphous solid water has been investigated at 157 nm. Using a resonance-enhanced multiphoton ionization technique, the translational and rotational energy distributions of photodesorbed H 2O( v = 0) were measured, i.e., Boltzmann distributions at 1800 and 300 K, respectively. These energies are in good accordance with those predicted by classical molecular calculations for water photodesorption due to a kick-out mechanism following absorption of a single photon; hot H atom released by photodissociation of H 2O in ice transfers enough momentum to another H 2O molecule to kick it off the surface. Desorption of D 2O( v = 0) following 193 nm photoirradiation of a D 2O/H 2S mixed ice was investigated to provide further direct evidence for the operation of a kick-out mechanism. The other desorption mechanisms were also discussed in the context of possible photodesorption of vibrationally excited H 2O.