Photodissociation Experiments Research Articles

Gas-Phase Characterization of Redox-Active Manganese Complexes.

Manganese complexes exhibit a rich redox chemistry, usually accompanied by structural reorganization during the redox processes often followed by ligand dissociation or association. The push-pull ligand 2,6-diguanidylpyridine (dgpy) stabilizes manganese in the oxidation states +II, +III, and + IV in the complexes [Mn(dgpy)2]n+ (n = 2-4) without change in the coordination sphere in the condensed phase [Heinze et al., Inorganic Chemistry, 2022, 61, 14616]. In the condensed phase, the manganese(IV) complex is a very strong oxidant. In the present work, we investigate the stability and redox activity of the MnIV complex and its counterion (PF6-) adducts in the gas phase, using two modified 3D Paul ion trap mass spectrometers. Six different cationic species of the type [Mnx(dgpy)2(PF6)y]n+ (x = II, III, IV, y = 0-3, n = 1-3) could be observed for the three oxidation states MnIV, MnIII, and MnII, of which one observed complex also contains a reduced dgpy ligand. MnII species showed the highest relative stability in collision induced dissociation and UV/vis photo dissociation experiments. The lowest stability is observed in the presence of one or more counterions, which correlates to a lower total charge n+. Gas phase UV/vis spectra show similar features as the condensed phase spectra only differing in relative band intensities. The strongly oxidizing MnIV complex reacts with triethylamine (NEt3) in the gas phase to give MnIII, while MnIII species show little reactivity toward NEt3.

Visible light induced generation of nitric oxide from designed ruthenium nitrosyl complex and studies on antibacterial activity

In this article, a chloro-bridged dinuclear ruthenium complex Ru-(a) has been synthesized, which was employed for the synthesis of a photolabile NO liberating complex Ru-(b). A newly synthesized tridentate ligand 2-methyl-6-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl)pyridine with three N-atoms as donating site was used to synthesize the complex Ru-(a). The molecular structure of Ru-(a) was investigated by single-crystal X-ray crystallography and, in solution was characterized by or ESI mass spectrometry. Several spectroscopic techniques were used for the characterization of the ligand as well as complexes. To understand the electronic structure of Ru-(a) and Ru-(b), DFT computations were utilized. By the utilization of visible light, photo-liberation experiments were examined. The amount of NO released during the photodissociation experiment was measured using the Griess reagent assay technique. The photodissociated NO was fruitfully transported to reduced myoglobin (Mb). The antibacterial activity against Escherichia coli was carried out with 31.2 μg/mL concentration of Ru-(b). In the final results, we detected considerable antibacterial activity against E. coli and showed >99 % inhibition of the bacterial cells after 120 min of the experiment on exposure to visible light. These investigations proposed that Ru-(b) could be employed to treat several topical deliveries of NO for treating various topical and bacterial infections.

Geometries and stabilities of chromium doped nitrogen clusters: mass spectrometry and density functional theory studies.

Metal-doped nitrogen clusters serve as effective models for elucidating the geometries and electronic properties of nitrogen-rich compounds at the molecular scale. Herein, we have conducted a systematic study of VIB-group metal chromium (Cr) doped nitrogen clusters through a combination of mass spectrometry techniques and density functional theory (DFT) calculations. The laser ablation is employed to generate CrNn+ clusters. The results reveal that CrN8+ cluster exhibits the highest signal intensity in mass spectrometry. The photodissociation experiments with 266 nm photons confirm that the chromium heteroazide clusters are composed of chromium ions and N2 molecules. Further structural searches and electronic structure calculations indicate that the cationic CrN8+ cluster possesses an X shaped geometry with D2 symmetry and exhibits robust stability. Molecular orbital and chemical bonding analyses demonstrate the existence of strong interactions between Cr+ cation and N2 ligands. The present findings enrich the geometries of metal doped nitrogen clusters and provide valuable guidance for the rational design and synthesis of novel transition metal nitrides.

Conformer-selective Photodynamics of TrpH+ -H2 O.

The photodynamics of protonated tryptophan and its mono hydrated complex TrpH+ -H2 O has been revisited. A combination of steady-state IR and UV cryogenic ion spectroscopies with picosecond pump-probe photodissociation experiments sheds new lights on the deactivation processes of TrpH+ and conformer-selected TrpH+ -H2 O complex, supported by quantum chemistry calculations at the DFT and coupled-cluster levels for the ground and excited states, respectively. TrpH+ excited at the band origin exhibits a transient of less than 100 ps, assigned to the lifetime of the excited state proton transfer (ESPT) structure. The two experimentally observed conformers of TrpH+ -H2 O have been assigned. A striking result arises from the conformer-selective photodynamics of TrpH+ -H2 O, in which a single water molecule inserted in between the ammonium and the indole ring hinders the barrierless ESPT reaction responsible for the ultra-fast deactivation process observed in the other conformer and in bare TrpH+ .

Observation of rotationally dependent fine-structure branching ratios near the predissociation threshold N(2D5/2,3/2) + N(2D5/2,3/2) of 14N2.

Photofragment spin-orbit fine-structure branching ratios have long been predicted to depend on the rotational quantum number J' by theory near the dissociation thresholds of several diatomic molecules, while this has rarely been observed in any photodissociation experiments yet. Here, we measured the fine-structure branching ratios N(2D5/2)/N(2D3/2) produced in the N(2D5/2,3/2) + N(2D5/2,3/2) channel at the b'1Σu +(v = 20) state of 14N2 by using our vacuum ultraviolet (VUV)-pump-VUV-probe time-sliced velocity-mapped ion imaging setup. It is found that 14N2 almost exclusively dissociates into the spin-orbit channel N(2D5/2) + N(2D3/2) at low rotational levels and gradually approaches the statistical or diabatic limit by distributing all possible spin-orbit channels at higher rotational levels. The strongly rotationally dependent fine-structure branching ratios should be due to the increasing strength of nonadiabatic Coriolis interaction among various dissociative states in the so-called "recoupling zone" as J' increases. They are supposed to provide unprecedented information on the near threshold photodissociation dynamics of 14N2.

TrapREMI: A reaction microscope inside an electrostatic ion beam trap

A new experimental setup has been developed to investigate the reactions of molecular ions and charged clusters with a variety of projectile beams. An Electrostatic Ion Beam Trap (EIBT) stores fast ions at keV energies in an oscillatory motion. By crossing it with a projectile beam, e.g., an IR laser, molecular reactions can be induced. We implemented a Reaction Microscope (REMI) in the field-free region of the EIBT to perform coincidence spectroscopy on the resulting reaction products. In contrast to prior experiments, this unique combination of techniques allows us to measure the 3D momentum-vectors of ions, electrons, and neutrals as reaction products in coincidence. At the same time, the EIBT allows for advanced target preparation techniques, e.g., relaxation of hot molecules during storage times of up to seconds, autoresonance cooling, and recycling of target species, which are difficult to prepare. Otherwise, the TrapREMI setup can be connected to a variety of projectile sources, e.g., atomic gas jets, large-scale radiation facilities, and ultrashort laser pulses, which enable even time-resolved studies. Here, we describe the setup and a first photodissociation experiment on H2 +, which demonstrates the ion-neutral coincidence detection in the TrapREMI.

Picosecond excited-state lifetimes of protonated indazole and benzimidazole: The role of the N-N bond.

Certain chemical groups give rise to characteristic excited-state deactivation mechanisms. Here, we target the role of a protonated N-N chemical group in the excited-state deactivation of protonated indazole by comparison to its isomer that lacks this group, protonated benzimidazole. Gas-phase protonated indazole and protonated benzimidazole ions are investigated at room temperature using picosecond laser pump-probe photodissociation experiments in a linear ion-trap. Excited state lifetimes are measured across a range of pump energies (4.0-5.4eV). The 1ππ* lifetimes of protonated indazole range from 390 ± 70ps using 4.0eV pump energy to ≤18ps using 4.6eV pump energy. The 1ππ* lifetimes of protonated benzimidazole are systematically longer, ranging from 3700 ± 1100ps at 4.6eV pump energy to 400 ± 200ps at 5.4eV. Based on these experimental results and accompanying quantum chemical calculations and potential energy surfaces, the shorter lifetimes of protonated indazole are attributed to πσ* state mediated elongation of the protonated N-N bond.

Photodissociation study of spatially oriented (R)-3-bromocamphor by the hexapole state selector

A photodissociation experiment of (R)-3-bromocamphor was carried out by the hexapole orientation technique by (2 + 1) REMPI detection at about 234 nm. The atomic bromine products in excited state (Br 2P1/2) and in ground state (Br 2P3/2) were observed by the velocity map imaging. The anisotropy parameters of Br (2P1/2) and Br (2P3/2) were obtained as 0.75 ± 0.04 and 0.48 ± 0.03, respectively. In addition, we also successfully controlled (R)-3-bromocamphor, the bulky and asymmetric bio-molecule’s, spatial orientation using the electrostatic hexapole. The orientational distribution was derived and its orientation efficiency was estimated as |<cos θ>|=0.35. We carried out a slice imaging experiment with the spatially oriented parent molecules to study the photodissociation dynamics of (R)-3-bromocamphor. The angular analysis of the obtained slice images suggests fast axial recoiling of the bromine atomic fragments and comparable contributions from the multiple upper states involved in A-band excitation, which results in the relatively isotropic angular distributions.

A compact electrostatic lens for velocity map imaging experiments

The traditional three-electrode Velocity Map Imaging (VMI) electrostatic lens developed by Eppink and Parker has proven to be a useful tool in a wide range of applications in molecular dynamics, including photodissociation experiments taking place in a molecular beam. However, in some other cases, such as crossed molecular beam experiments, the large diameter (typically ∼70 mm) of this conventional VMI lens can be inconvenient. We describe here a VMI lens with a much smaller diameter (down to ∼20 mm) using tubular electrodes. The performance is evaluated by imaging O+ fragments produced by the photodissociation of O2 at around 225 nm, and by inelastic scattering of NO with Ar. Our results suggest that the recorded images are of acceptable quality compared to those from a standard lens while achieving a fourfold reduction of the VMI lens diameter.

Simulation of the effect of vibrational pre-excitation on the dynamics of pyrrole photo-dissociation.

Photo-dissociation dynamics is simulated for vibrationally pre-excited pyrrole molecules using an ab initio multiple cloning approach. Total kinetic energy release (TKER) spectra and dissociation times are calculated. It is found that pre-excitation of N-H bond vibrations facilitates fast direct dissociation, which results in a significant increase in the high-energy wing of TKER spectra. The results are in very good agreement with the recent vibrationally mediated photo-dissociation experiment, where the TKER spectrum was measured for pyrrole molecules excited by a combination of IR and UV laser pulses. Calculations for other vibrational modes show that this effect is specific for N-H bond vibrations: Pre-excitation of other modes does not result in any significant changes in TKER spectra.

Ion-neutral photofragment coincidence imaging of photodissociation dynamics of ionic species

The recently constructed cryogenic cylindrical ion trap velocity map imaging spectrometer (CIT-VMI) has been upgraded for coincidence imaging of both ionic and neutral photofragments from photodissociation of ionic species. The prepared ions are cooled down in a home-made cryogenic cylindrical ion trap and then extracted for photodissociation experiments. With the newly designed electric fields for extraction and acceleration, the ion beam can be accelerated to more than 4500 eV, which is necessary for velocity imaging of the neutral photofragments by using the position-sensitive imaging detector. The setup has been tested by the 355 nm photodissociation dynamics of the argon dimer cation (Ar2+). From the recorded experimental images of both neutral Ar and ionic Ar+ fragments, we interpret velocity resolutions of Δv/v≈4.6% for neutral fragments, and Δv/v≈1.5% for ionic fragments, respectively.

Mammal hyaluronidase activity on chondroitin sulfate and dermatan sulfate: Mass spectrometry analysis of oligosaccharide products.

Mammalian hyaluronidases are endo-N-acetyl-D-hexosaminidases involved in the catabolism of hyaluronic acid (HA) but their role in the catabolism of chondroitin sulfate (CS) is also examined. HA and CS are glycosaminoglycans implicated in several physiological and pathological processes, and understanding their metabolism is of significant importance. Data have been previously reported on the degradation of CS under the action of hyaluronidase, yet a detailed structural investigation of CS depolymerization products remains necessary to improve our knowledge of the CS depolymerizing activity of hyaluronidase. For that purpose, the fine structural characterization of CS oligosaccharides formed upon the enzymatic depolymerization of various CS subtypes by hyaluronidase has been carried out by high-resolution Orbitrap mass spectrometry (MS) and extreme UV (XUV) photodissociation tandem MS. The exact mass measurements show the formation of wide size range of even oligosaccharides upon digestion of CS-A and CS-C comprising hexa- and octa-saccharides among the main digestion products, as well as formation of small quantities of odd-numbered oligosaccharides, while no hyaluronidase activity was detected on CS-B. In addition, slight differences have been observed in the distribution of oligosaccharides in the digestion mixture of CS-A and CS-C, the contribution of longer oligosaccharides being significantly higher for CS-C. The sequence of CS oligosaccharide products determined XUV photodissociation experiments verifies the selective β(1→4) glycosidic bond cleavage catalyzed by mammal hyaluronidase. The ability of the mammal hyaluronidase to produce hexa- and higher oligosaccharides supports its role in the catabolism of CS anchored to membrane proteoglycans and in extra-cellular matrix.

Ab initio dynamics simulation of laser-induced photodissociation of phenol.

We theoretically investigated the photodissociation dynamics of phenol molecules steered by a sequence of temporally shaped femtosecond laser pulses with high intensity and ultrashort duration, via the real-time Time-Dependent Density Functional Theory (rt-TDDFT) combined with a Molecular Dynamics (MD) simulation. The principal findings of this research are that the phenol photodissociation can take place in 50 fs; the bonds broke sequentially; the degree of phenol molecular dissociation has a strong linear correlation with the intensity. For an incident laser being 800 nm-40 fs (wavelength-pulse duration), the threshold intensity is 7 × 1014 W cm-2 and the products are hydrogen from OH1 (phenolic hydroxyl group) and C6H5O-fragments. More fragments will be found at stronger intensity, shorter wavelengths, and longer pulse duration. More accurately, we estimated the critical values of bond cleavage of an isolated phenol molecule are 1.779 Å for O-H1 and 2.184 Å for C-Hs via Electron localization function (ELF) analysis. The photodissociation of the phenol molecule was triggered via the excitation of electrons and the dissociation process of phenol here is in good agreement with the characteristics of field-assisted dissociation (FAD) theory. Orthogonal tests with an L9 (34) matrix and threshold intensity decrease tests were conducted to confirm the mechanism. Our research gives an insight into the photodissociation experiment of phenol and provides a simple yet effective way to understand the photochemical experiments of more complex organic pollutants with toxicity.

Wavelength-Dependent Ultraviolet Photodissociation of Protonated Tryptamine.

Ultraviolet photodissociation (UVPD) experiments of protonated tryptamine ([Tryp+H]+) have been implemented by a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer combined with a wavelength-tunable optical parametric oscillator (OPO) laser. UVPD mass spectra under different laser wavelengths have been obtained, in which the dependence of the yield of fragment ions on the laser wavelength was observed. The UVPD spectrum of [Tryp+H]+ has been obtained in the range of 210-310 nm. Besides the previously reported two competitive channels of H loss and NH3 loss, two important channels of losing CH2NH and CH2NH2 units were observed and further studied by UV-UV tandem mass spectrometry and theoretical calculations. Interestingly, results show that the pair of competitive channels of CH2NH loss and CH2NH2 loss are both from the McLafferty-type rearrangement caused by ππ* electronic excited states. After the excitation, the two different dissociation pathways produce two different ion-neutral complexes, respectively. The wavelength-dependent dissociation and the existing competitive channels shown in this study reflect the diversity of UVPD processes of such organic molecules.

Ligand pathways in neuroglobin revealed by low-temperature photodissociation and docking experiments.

A combined biophysical approach was applied to map gas-docking sites within murine neuroglobin (Ngb), revealing snapshots of events that might govern activity and dynamics in this unique hexacoordinate globin, which is most likely to be involved in gas-sensing in the central nervous system and for which a precise mechanism of action remains to be elucidated. The application of UV-visible microspectroscopy in crystallo, solution X-ray absorption near-edge spectroscopy and X-ray diffraction experiments at 15-40 K provided the structural characterization of an Ngb photolytic intermediate by cryo-trapping and allowed direct observation of the relocation of carbon monoxide within the distal heme pocket after photodissociation. Moreover, X-ray diffraction at 100 K under a high pressure of dioxygen, a physiological ligand of Ngb, unravelled the existence of a storage site for O2 in Ngb which coincides with Xe-III, a previously described docking site for xenon or krypton. Notably, no other secondary sites were observed under our experimental conditions.

Quantum state-to-state vacuum ultraviolet photodissociation dynamics of small molecules

The present review focused on selected, recent experimental progress of photodissociation dynamics of small molecules covering the vacuum ultraviolet (VUV) range from 6 eV to 20 eV. These advancements come about due to the available laser based VUV light sources, along with the developments of advanced experimental techniques, including the velocity-map imaging (VMI), H-atom Rydberg tagging time-of-flight (HRTOF) techniques, as well as the two-color tunable VUV-VUV laser pump-probe detection method. The applications of these experimental techniques have allowed VUV photodissociation studies of many diatomic and triatomic molecules to quantum state-to-state in detail. To highlight the recent accomplishments, we have summarized the results on several important molecular species, including H2 (D2, HD), CO, N2, NO, O2, H2O (D2O, HOD), CO2, and N2O. The detailed VUV photodissociation studies of these molecules are of astrochemical and atmospheric relevance. Since molecular photodissociation initiated by VUV excitation is complex and is often governed by multiple electronic potential energy surfaces, the unraveling of the complex dissociation dynamics requires state-to-state cross section measurements. The newly constructed Dalian Coherent Light Source (DCLS), which is capable of generating coherent VUV radiation with unprecedented brightness in the range of 50–150 nm, promises to propel the photodissociation experiment to the next level.

Fast beam photofragment translational spectroscopy of the phenoxy radical at 225 nm, 290 nm, and 533 nm.

Photodissociation of the phenoxy radical (C6H5O) is investigated using fast beam photofragment translational spectroscopy. Phenoxy radicals are generated through photodetachment of phenoxide anions (C6H5O-) at 532 nm. Following photoexcitation of the radicals at 225 nm (5.51 eV), 290 nm (4.27 eV), or 533 nm (2.33 eV), photofragments are collected in coincidence to determine their masses, translational energy, and scattering angle for each dissociation event. Two-body dissociation yields exclusively CO + C5H5, and three-body dissociation to CO + C2H2 + C3H3 and CO + C5H4 + H is also seen at the two higher energies. The translational energy distributions for two-body dissociation suggest that dissociation occurs via internal conversion to the ground electronic state followed by statistical dissociation. The absorption of an additional 532 nm photon in the photodetachment region provides some C6H5O radicals with an additional 2.33 eV of energy, leading to much of the two-body dissociation observed at 533 nm and the three-body dissociation at the two higher excitation energies.

Mapping the intrinsic absorption properties and photodegradation pathways of the protonated and deprotonated forms of the sunscreen oxybenzone.

Sunscreens provide vital protection against the photodamaging effects of UV radiation, however, many fundamental questions remain about the detailed mechanisms by which they dissipate UV energy. One such issue is the extent to which the pH environment of an organic sunscreen molecule alters its effectiveness, both in terms of ability to absorb UV radiation, and also its potential to photodegrade. Here, we use gas-phase laser photodissociation spectroscopy for the first time to measure the intrinsic UVA-UVC absorption spectra and associated photodegradation products of protonated and deprotonated oxybenzone, away from the complications of bulk mixtures. Our results reveal that protonation state has a dramatic effect on the absorption and photodissociation properties of this sunscreen. While the UV absorption profile of oxybenzone is only modestly affected by protonation across the range from 400-216 nm, deprotonated oxybenzone displays a significantly modified absorption spectrum, with very low photoabsorption between 370-330 nm. Protonated oxybenzone primarily photofragments by rupture of the bonds on either side of the central carbonyl group, producing cationic fragments with m/z 151 and 105. Additional lower mass photofragments (e.g. m/z 95 and 77) are also observed. The production spectra for the photofragments from protonated oxybenzone fall into two distinct categories, which we discuss in the context of different excited state decay pathways. For deprotonated oxybenzone, the major photofragments observed are m/z 211 and 212, which are associated with the ejection of methane and the methyl free radical from the parent ion, respectively. Implications for the suitability of oxybenzone in its protonated and deprotonated forms as an optimum sunscreen molecule are discussed.

Mass Spectrometry and Theoretical Investigation of VN n+ ( n = 8, 9, and 10) Clusters.

VN n+ clusters were generated by laser ablation and analyzed by mass spectrometry. The results showed that VN8+, VN9+, and VN10+ clusters were formed, and the mass peak of VN8+ is dominant in the spectrum. The VN8+ cluster was further investigated by a photodissociation experiment with 266 nm photons. Density functional theory calculations were conducted at the M06-2X/6-311+G(d,p) level to search for stable structures of VN n+ ( n = 8, 9, and 10) and their neutral counterparts. The theoretical calculations revealed that the most stable structure of VN8+ is in the form of V(N2)4+ with D 4h symmetry. The binding energy from the calculation is in good agreement with that obtained from the photodissociation experiments. The global minimum structures of VN8, VN9+/0, and VN10+/0 contain a similar substructure of the N4 ring and exhibit energy properties. The most stable structure of VN9+ is in the form of (η2-N4)V+N(N2)2 with C1 symmetry, while that of VN10+ is in the form of (η4-N4)V+(N2)3 with C s symmetry. For neutral VN8, VN9, and VN10, (η4-N4)V(N2)2, (η4-N4)V(N3)(N2), and (η4-N4)V(N2)3 are their ground-state structures, with decomposition into one V atom, and corresponding quantities of N2 can release energies of about 50.20, 96.28, and 57.76 kcal/mol, respectively.

Effects of wavelength, fluence, and dose on fragmentation pathways and photoproduct ion yield in 213 nm and 266 nm ultraviolet photodissociation experiments.

Ultraviolet photodissociation tandem mass spectrometry is a powerful tool to investigate the structure of biomolecules, due to its ability to generate rich fragmentation patterns or bond selective cleavage, as a function of used laser wavelength, laser fluence, dose (number of accumulated laser pulses), and available chromophores. Herein, we report first results obtained with a newly developed two-wavelength (266 nm and 213 nm) ultraviolet photodissociation setup coupled to a Fourier-transform ion cyclotron resonance mass spectrometer. Photoproduct yields for protonated 3-iodo-l-tyrosine were up to ∼75%. Dose and fluence dependent measurements for protonated 3-iodo-l-tyrosine, doubly charged protonated bradykinin and Fe(II) attached to 1,2-dioleoyl-sn-glycero-3-phosphocholine reveal that the ultraviolet photodissociation mechanism for photoproduct formation qualitatively differs between these model systems. Three derived photodissociation models were used to interpret the experimental results and show that while protonated 3-iodo-l-tyrosine and Fe(II) attached to 1,2-dioleoyl-sn-glycero-3-phosphocholine most likely dissociates via a single-photon process, fragmentation of doubly charged bradykinin ions was found to be most consistent with sequential two-photon dissociation (213 nm). The introduced dissociation models present an easy means to study the mechanism of ultraviolet photodissociation processes for a variety of analytes without prior knowledge of their photochemistry or to optimize experimental conditions by adjusting laser fluence or number of laser pulses.