Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability.

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O …H … OCO) features a single local minima, with the proton localized on the O group (OH… OCO).

Pre-Dewar structure modulates protonated azaindole photodynamics.

Recent experimental work revealed that the lifetime of the S state of protonated 7-azaindole is about ten times longer than that of protonated 6-azaindole. We simulated the nonradiative decay pathways of these molecules using trajectory surface hopping dynamics after photoexcitation into S to elucidate the reason for this difference. Both isomers mainly follow a common ππ* relaxation pathway involving multiple state crossings while coming down from S to S in the subpicosecond time scale.

Loss of CO from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment.

The decarboxylation (CO loss) mechanism of cold monodeprotonated phthalic acid was studied in a photodissociation action spectrometer by quantifying mass-selected product anions and neutral particles as a function of the excitation energy. The analysis proceeded by interpreting the translational energy distribution of the generated uncharged products, and with the help of quantum calculations. In particular, this study reveals different fragmentation pathways in the deprotonated anion and in the radical generated upon electron photodetachment.

Non-destructive detection of large molecules without mass limitation.

The problem for molecular identification knows many solutions, which include mass spectrometers whose mass sensitivity depends on the performance of the detector involved. The purpose of this article is to show by means of molecular dynamics simulations how a laser-cooled ion cloud, confined in a linear radio-frequency trap, can reach the ultimate sensitivity providing the detection of individual charged heavy molecular ions. In our simulations, we model the laser-cooled Ca ions as two-level atoms, confined thanks to a set of constant and time oscillating electrical fields.

Revealing the role of excited state proton transfer (ESPT) in excited state hydrogen transfer (ESHT): systematic study in phenol-(NH) clusters.

Excited State Hydrogen Transfer (ESHT), proposed at the end of the 20th century by the corresponding authors, has been observed in many neutral or protonated molecules and become a new paradigm to understand excited state dynamics/photochemistry of aromatic molecules. For example, a significant number of photoinduced proton-transfer reactions from X-H bonds have been re-defined as ESHT, including those of phenol, indole, tryptophan, aromatic amino acid cations and so on. Photo-protection mechanisms of biomolecules, such as isolated nucleic acids of DNA, are also discussed in terms of ESHT.

Influence of the N atom and its position on electron photodetachment of deprotonated indole and azaindole.

Electron photodetachment of cold deprotonated indole and azaindole anions has been studied by use of a mass-selective photofragmentation spectrometer capable of negative ion and neutral particle detection. The electron affinities of the indolyl radical and the 5-, 6- and 7-azaindolyl radicals have been measured with an uncertainty of less than 0.002 eV.

Influence of the N atom position on the excited state photodynamics of protonated azaindole.

We present a study of the photofragmentation of three protonated azaindole molecules - 7-azaindole, 6-azaindole, and 5-azaindole - consisting of fused pyrrole-pyridine bicyclic aromatic systems, in which the pyridinic (protonated) nitrogen heteroatom is located at the 7, 6, and 5 positions, respectively. Photofragmentation electronic spectra of the isolated aforementioned azaindolinium cations reveal that their photodynamics extends over timescales covering nine orders of magnitude and provide evidence about the resultant fragmentation pathways. Moreover, we show how the position of the heteroatom in the aromatic skeleton influences the excited state energetics, fragmentation pathways, and fragmentation timescales.

Photoinduced water oxidation in pyrimidine-water clusters: a combined experimental and theoretical study.

The photocatalytic oxidation of water with molecular or polymeric N-heterocyclic chromophores is a topic of high current interest in the context of artificial photosynthesis, that is, the conversion of solar energy to clean fuels. Hydrogen-bonded clusters of N-heterocycles with water molecules in a molecular beam are simple model systems for which the basic mechanisms of photochemical water oxidation can be studied under well-defined conditions. In this work, we explored the photoinduced H-atom transfer reaction in pyrimidine-water clusters yielding pyrimidinyl and hydroxyl radicals with laser spectroscopy, mass spectrometry and trajectory-based ab initio molecular dynamics simulations.

Excited state hydrogen transfer dynamics in phenol-(NH) studied by picosecond UV-near IR-UV time-resolved spectroscopy.

Time-evolutions of excited state hydrogen transfer (ESHT) in phenol (PhOH)-(NH) clusters have been measured by three-color picosecond (ps) ultraviolet (UV)-near infrared (NIR)-UV pump-probe ion dip spectroscopy. The formation of a reaction product, ˙NHNH, is detected by its NIR absorption due to a 3p-3s Rydberg transition. The ESHT reactions from all of the vibronic levels show biexponential time-evolutions, even from the S origin.

Photodetachment of deprotonated aromatic amino acids: stability of the dehydrogenated radical depends on the deprotonation site.

While aromatic amino acids in their deprotonated form have been well characterized by IR and photoelectron spectroscopies, no information is available on the neutral dehydrogenated radicals and, in particular, on their stability when the deprotonation site is changed. This is investigated by observing the neutral fragment issued from either simple photodetachment or dissociative photodetachment of the deprotonated aromatic amino acids phenylalanine, tyrosine, and tryptophan. We show that the dehydrogenated radicals of aromatic amino acids produced upon photodetachment of molecules deprotonated on the carbonyl group dissociate without barrier, leading to the formation of CO and a radical amine.

UV Photoinduced Dynamics of Conformer-Resolved Aromatic Peptides.

A detailed understanding of radiative and nonradiative processes in peptides containing an aromatic chromophore requires the knowledge of the nature and energy level of low-lying excited states that could be coupled to the bright ππ* excited state. Isolated aromatic amino acids and short peptides provide benchmark cases to study, at the molecular level, the photoinduced processes that govern their excited state dynamics. Recent advances in gas phase laser spectroscopy of conformer-selected peptides have paved the way to a better, yet not fully complete, understanding of the influence of intramolecular interactions on the properties of aromatic chromophores.

Dissociative photodetachment vs. photodissociation of aromatic carboxylates: the benzoate and naphthoate anions.

The competition between dissociative photodetachment and photodissociation of cold benzoate and naphthoate anions was studied through measurement of the kinetic energy of the neutral fragments and intact parent benzoyloxy and naphtoyloxy radicals as well as by detecting the anionic fragments whenever they are produced. For the benzoate anion, there is no ionic photodissociation and the radical dissociation occurs near the vertical photodetachment energy. This is in agreement with DFT calculations showing that the dissociation energy in CO2 and C6H5˙ is very low.

Pseudorotaxanes in the gas phase: structure and energetics of protonated dibenzylamine-crown ether complexes.

We observe UV spectra of protonated dibenzylamine (dBAMH+) and its complexes with 15-crown-5 (dBAMH+-15C5), 18-crown-6 (dBAMH+-18C6), and 24-crown-8 (dBAMH+-24C8) under cold (∼10 K) gas-phase conditions by UV photodissociation (UVPD) and UV-UV hole-burning (HB) spectroscopy. The UVPD spectrum of the dBAMH+-15C5 complex shows an extensive low-frequency progression, which originates from a unique conformation of the dBAMH+ part with benzene rings facing closely to each other, while UVPD and calculation results suggest open conformations of the dBAMH+ part for dBAMH+-18C6 and dBAMH+-24C8. UV-UV HB spectra of the dBAMH+-24C8 complex indicate that there exist at least two conformers; multiple conformations can contribute to high stability of dBAMH+-24C8 pseudorotaxane due to "conformational" entropic effects.

Tautomerism and electronic spectroscopy of protonated 1- and 2-aminonaphthalene.

Experimental and theoretical investigations of the excited states of protonated 1- and 2-aminonaphthalene are presented. The electronic spectra are obtained by laser induced photofragmentation of the ions captured in a cold ion trap. Using ab initio calculations, the electronic spectra can be assigned to different tautomers which have the proton on the amino group or on the naphthalene moiety.

Electron-Proton Transfer Mechanism of Excited-State Hydrogen Transfer in Phenol-(NH ) (n=3 and 5).

Excited-state hydrogen transfer (ESHT) is responsible for various photochemical processes of aromatics, including photoprotection of nuclear basis. Its mechanism is explained by internal conversion from the aromatic ππ* to πσ* states via conical intersection. This means that the electron is transferred to a diffuse Rydberg-like σ* orbital apart from proton migration.

Electronic spectrum of the protonated diacetylene cation (HCH).

The B̃A←X̃A electronic band system of the protonated diacetylene cation (HCH) is measured over the 230-295 nm range by photodissociating HCH ions stored in a cryogenic ion trap and by photodissociating HCH tagged with Ar and N in a tandem mass spectrometer. The B̃A←X̃A band system has an origin at 34 941 cm for HCH, 34 934 cm for HCH-Ar, and 34 920 cm for HCH-N. The spectra of HCH, HCH-Ar, and HCH-N display similar vibronic structure, which is assigned using ab initio calculations to progressions in two symmetric a C-C stretch vibrational modes (ν and ν), with band spacings of 860 and 1481 cm, respectively.

Excited State Dynamics of Cold Protonated Cytosine Tautomers: Characterization of Charge Transfer, Intersystem Crossing, and Internal Conversion Processes.

Charge transfer reactions are ubiquitous in chemical reactivity and often viewed as ultrafast processes. For DNA, femtochemistry has undeniably revealed the primary stage of the deactivation dynamics of the locally excited state following electronic excitation. We here demonstrate that the full time scale excited state dynamics can be followed up to milliseconds through an original pump-probe photodissociation scheme applied to cryogenic ion spectroscopy.

Electronic Spectroscopy of Protonated 1-Aminopyrene in a Cold Ion Trap.

In aromatic systems that contain an amino group, there is competition between protonation on a carbon atom of the skeleton and protonation on the amino group. Herein, we studied the photofragmentation of protonated 1-aminopyrene in a cold ion trap and mainly observed the protonated amino tautomer, which led to fragmentation pathways through the loss of H or NH groups. Several excited states were assigned, among which the fourth excited state showed broadened bands, thus indicating a fast decay that was attributed to the presence of a πσ* charge-transfer state by comparison of the experimental results with ab initio calculations.

Photodissociation Electronic Spectra of Cold Protonated Quinoline and Isoquinoline in the Gas Phase.

Photofragmentation electronic spectra of isolated single-isomeric N-protonated quinoline (quinolinium) and isoquinoline (isoquinolinium) ions have been measured at a temperature of ∼40 K using a mass-selective, 10 cm spectral resolution, photodissociation spectrometer. Additionally, ab initio adiabatic transition energies calculated using the RI-ADC(2) method have been employed to assist in the assignment of the spectra. Three electronic transitions having ππ* character were clearly evidenced for both protonated ions within the UV and deep-UV spectral ranges.

A conformational study of protonated noradrenaline by UV-UV and IR dip double resonance laser spectroscopy combined with an electrospray and a cold ion trap method.

The conformer-selected ultraviolet (UV) and infrared (IR) spectra of protonated noradrenaline were measured using an electrospray/cryogenic ion trap technique combined with photo-dissociation spectroscopy. By comparing the UV photo dissociation (UVPD) spectra with the UV-UV hole burning (HB) spectra, it was found that five conformers coexist under ultra-cold conditions. Based on the spectral features of the IR dip spectra of each conformer, two different conformations on the amine side chain were identified.

Hydrogen bonds vs. π-stacking interactions in the p-aminophenolp-cresol dimer: an experimental and theoretical study.

The gas phase structure and excited state lifetime of the p-aminophenolp-cresol heterodimer have been investigated by REMPI and LIF spectroscopy with nanosecond laser pulses and pump-probe experiments with picosecond laser pulses as a model system to study the competition between π-π and H-bonding interactions in aromatic dimers. The excitation is a broad and unstructured band. The excited state of the heterodimer is long lived (2.

Photoinduced water splitting in pyridine water clusters.

Ab initio calculations predict that pyridine (Py) can act as a photo-catalyst to split water by the absorption of a UV photon following the reaction Py-HO + hν → PyH˙ + OH˙. To test this prediction, we performed two types of experiments: in the first, we characterize the electronic spectroscopy of the PyH˙ radical in the gas phase. In the second, we evidence the reaction through the UV excitation of molecular Py-(HO) clusters obtained in a supersonic expansion and monitoring the PyH˙ reaction product.

Photodissociation UV-Vis Spectra of Cold Protonated Azobenzene and 4-(Dimethylamino)azobenzene and Their Benzenediazonium Cation Fragment.

Gas phase photodissociation electronic spectra of protonated azobenzene (ABH(+)) and 4-(dimethylamino)azobenzene (dmaABH(+)) were measured in a cryogenically cooled ion trap at temperatures of a few tens of Kelvin. Experimental results were complemented with electronic structure calculations in the ground state at the MP2/cc-pVDZ level of theory, and in the low lying excited states using the RI-CC2 method. Calculated energies revealed that only the trans isomers of the azonium molecular ions (protonation site on the azo group) will likely exist in the trap at the temperatures achieved in the experiment.

Twisted Intramolecular Charge Transfer in Protonated Amino Pyridine.

The excited state properties of protonated ortho (2-), meta (3-), and para (4-) aminopyridine molecules have been investigated through UV photofragmentation spectroscopy and excited state coupled-cluster CC2 calculations. Cryogenic ion spectroscopy allows recording well-resolved vibronic spectroscopy that can be reproduced through Franck-Condon simulations of the ππ* local minimum of the excited state potential energy surface. The excited state lifetimes have also been measured through a pump-probe excitation scheme and compared to the estimated radiative lifetimes.

Non-radiative processes in protonated diazines, pyrimidine bases and an aromatic azine.

The excited state lifetimes of DNA bases are often very short due to very efficient non-radiative processes assigned to the ππ*-nπ* coupling. A set of protonated aromatic diazine molecules (pyridazine, pyrimidine and pyrazine C4H5N2(+)) and protonated pyrimidine DNA bases (cytosine, uracil and thymine), as well as the protonated pyridine (C5H6N(+)), have been investigated. For all these molecules except one tautomer of protonated uracil (enol-keto), electronic spectroscopy exhibits vibrational line broadening.