Time-resolved photoelectron imaging of the chloranil radical anion: ultrafast relaxation of electronically excited electron acceptor states

The spectroscopy and dynamics of near-threshold excited states of the isolated chloranil radical anion are investigated using photoelectron imaging. The photoelectron images taken at 480 nm clearly indicate resonance-enhanced photodetachment via a bound electronic excited state. Time-resolved photoelectron imaging reveals that the excited state rapidly decays on a timescale of 130 fs via internal conversion. The ultrafast relaxation dynamics of excited states near threshold are pertinent to common electron acceptor molecules based on the quinone moiety and may serve as doorway states that enable efficient electron transfer in the highly exergonic inverted regime, despite the presence of large free energy barriers.     

Direct observation of a sulfonyl azide excited state and its decay processes by ultrafast time-resolved IR spectroscopy

The photochemistry of 2-naphthylsulfonyl azide (2-NpSO(2)N(3)) was studied by femtosecond time-resolved infrared (TR-IR) spectroscopy and with quantum chemical calculations. Photolysis of 2-NpSO(2)N(3) with 330 nm light promotes 2-NpSO(2)N(3) to its S(1) state. The S(1) excited state has a prominent azide vibrational band. This is the first direct observation of the S(1) state of a sulfonyl azide, and this vibrational feature allows a mechanistic study of its decay processes. The S(1) state decays to produce the singlet nitrene. Evidence for the formation of the pseudo-Curtius rearrangement product (2-NpNSO(2)) was inconclusive. The singlet sulfonylnitrene (1)(2-NpSO(2)N) is a short-lived species (τ ≈ 700 ± 300 ps in CCl(4)) that decays to the lower-energy and longer-lived triplet nitrene (3)(2-NpSO(2)N). Internal conversion of the S(1) excited state to the ground state S(0) is an efficient deactivation process. Intersystem crossing of the S(1) excited state to the azide triplet state contributes only modestly to deactivation of the S(1) state of 2-NpSO(2)N(3).     

Ab initio study of a biradical radiationless decay channel of the lowest excited electronic state of cytosine and its derivatives

A theoretical model for the ultrafast S1-->S0 internal conversion of cytosine is presented, in which a state switch from the initially prepared 1pipi* state to the out-of-plane deformed excited state of biradical character controls the rate of the S1(1pipi*) decay. This mechanism successfully accounts for the dramatically longer S1 lifetimes of 5-fluorocytosine and N-acetylcytosine relative to cytosine. The replacement of the C5 hydrogen atom by a methyl group is predicted to lead to a substantial, but not dramatic, increase in the S1 lifetime, also consistent with experiment. It is this ability to correctly predict the substituent effects that distinguishes the present model from the previously proposed mechanisms.     

Thermochemistry of N-N containing ions: a threshold photoelectron photoion coincidence spectroscopy study of ionized methyl- and tetramethylhydrazine

The unimolecular dissociation reactions of the methylhydrazine (MH) and tetramethylhydrazine (TMH) radical cations have been investigated using tandem mass spectrometry and threshold photoelectron photoion coincidence spectroscopy in the photon energy ranges 9.60-31.95 eV (for the MH ion) and 7.74-29.94 eV (for the TMH ion). Methylhydrazine ions (CH3NHNH2(+*)) have three low-energy dissociation channels: hydrogen atom loss to form CH2NHNH2(+) (m/z 45), loss of a methyl radical to form NHNH2(+) (m/z 31), and loss of methane to form the fragment ion m/z 30, N2H2(+*). Tetramethylhydrazine ions only exhibit two dissociation reactions near threshold: that of methyl radical loss to form (CH3)2NNCH3(+) (m/z 73) and of methane loss to form the fragment ion m/z 72 with the empirical formula C3H8N2(+*). The experimental breakdown curves were modeled with Rice-Ramsperger-Kassel-Marcus theory, and it was found that, particularly for methyl radical loss, variational transition state theory was needed to obtain satisfactory fits to the data. The 0 K enthalpies of formation (delta(f)H0) for all fragment ions (m/z 73, m/z 72, m/z 45, m/z 31, and m/z 30) have been determined from the 0 K activation energies (E0) obtained from the fitting procedure: delta(f)H0[(CH3)2NNCH3(+)] = 833 +/- 5 kJ mol(-1), delta(f)H0 [C3H8N2(+*)] = 1064 +/- 5 kJ mol(-1), delta(f)H0[CH2NHNH2(+)] = 862 +/- 5 kJ mol(-1), delta(f)H0[NHNH2(+)] = 959 +/- 5 kJ mol(-1), and delta(f)H0[N2H2(+*)] = 1155 +/- 5 kJ mol(-1). The breakdown curves have been measured from threshold up to h nu approximately 32 eV for both hydrazine ions. As the photon energy increases, other dissociation products are observed and their appearance energies are reported.     

Highly effective quenching of the ultrafast radiationless decay of photoexcited pyrimidine bases by covalent modification: photophysics of 5,6-trimethylenecytosine and 5,6-trimethyleneuracil

5,6-Trimethylenecytosine (TMC) and 5,6-trimethyleneuracil (TMU), in which the twist of the C5-C6 bond (or the pyrimidalization of C5) is strongly hindered, do not exhibit the subpicosecond excited-state lifetime characteristic of the naturally occurring pyrimidine bases. This result demonstrates the important role the out-of-plane deformation of the six-membered ring plays in the ultrafast (subpicosecond) internal conversion of photoexcited nucleobases. The dramatically shorter fluorescence lifetime of TMU ( approximately 30 ps) relative to TMC ( approximately 1.2 ns), in aqueous solution at room temperature, is attributed to the presence in TMU of an efficient, secondary nonradiative decay channel of S(1)(pipi*) involving a low-lying (1)npi* state.     

Monitoring the effect of ultrafast deactivation of the electronic excited states of DNA bases and polynucleotides following 267 nm laser excitation using picosecond time-resolved infrared spectroscopy

In this paper we demonstrate the use of picosecond time-resolved infrared spectroscopy (ps-TRIR) to monitor the early structural dynamics of DNA bases and polydeoxynucleotides following UV excitation in solution.     

A TDDFT study of the excited states of DNA bases and their assemblies

We present a detailed study of the optical absorption spectra of DNA bases and base pairs, carried out by means of time dependent density functional theory. The spectra for the isolated bases are compared to available theoretical and experimental data and used to assess the accuracy of the method and the quality of the exchange-correlation functional. Our approach turns out to be a reliable tool to describe the response of the nucleobases. Furthermore, we analyze in detail the impact of hydrogen bonding and pi-stacking in the calculated spectra for both Watson-Crick base pairs and Watson-Crick stacked assemblies. We show that the reduction of the UV absorption intensity (hypochromicity) for light polarized along the base-pair plane depends strongly on the type of interaction. For light polarized perpendicular to the basal plane, the hypochromicity effect is reduced, but another characteristic is found, namely a blue shift of the optical spectrum of the base-assembly compared to that of the isolated bases. The use of optical tools as fingerprints for the characterization of the structure (and type of interaction) is extensively discussed.     

Ab initio study of the ionization of the DNA bases: ionization potentials and excited states of the cations

The ionization of the four DNA bases is investigated by means of ab initio calculations. Accurate values of the gas-phase vertical and adiabatic ionization potentials (IP) are obtained at the MP2/6-31G(2d(0.8,alpha(d)),p) level of theory. The need of introducing extra polarization to the standard 6-31G(d,p) basis set is demonstrated by test calculations and an optimal value of alpha(d) = 0.1 is obtained. Ionization to electronically excited radical cations is also considered. The low-lying excited states of the cations are characterized for the first time. The topology of the corresponding potential energy surfaces is qualitatively described in terms of the stationary points (minima and saddle points) located on these surfaces. A conical intersection is characterized for the first time on the ground-state potential energy surface of all cations. It arises from the crossing of the adiabatic surfaces of the ground and first excited state at planar geometries. A nonplanar minimum is observed for the cytosine cation only. The geometry and electronic changes occurring along these surfaces are analyzed, leading to a comparison between the different nucleobase cations. The study of larger ionized systems related to DNA is rendered possible thanks to the optimized medium size basis set proposed in this work, as exemplified by the calculation of the IP of a stacked dimer of guanines.     

Unimolecular dissociations of excited C3H6O+: A photoelectron—photoion coincidence study of cyclopropanol and allyl alcohol

The photoelectron spectrum of cyclopropanol has been determined and the first few bands have been assigned to the respective ionization processes. The dissociative photoionization of cyclopropanol and allyl alcohol has been studied by means of HeIα photoelectron—photoion coincidence spectroscopy. The breakdown diagrams of the two corresponding radical cations are practically indistinguishable within the entire energy range investigated (= 5 eV). This implies that extensive isomerizations to a single or to a mixture of common precursor structure(s) precede the dissociative processes. The currently available information on the structure of this reactant and, in particular, the role of other C₃H₆O⁺ isomers is discussed. The kinetic and thermodynamic aspects of the present results are outlined. Although three generations of daughter ions are involved, the relative importance of the different fragmentation pathways could be determined. The RRKM analysis of the coincidence data suggests that the formation of the ethylene cation by loss of a CO molecule from the parent ion hardly competes with the other four primary fragmentation reactions in the sense of the statistical theory of unimolecular reactions.     

Unimolecular dissociations of excited C3H6O+: A comparative photoelectron—photoion coincidence study of 1,2-epoxypropane and acetone

The unimolecular fragmentation of internal energy selected 1,2-epoxypropane cations has been studied by fixed-wavelength photoelectron—photoion coincidence spectroscopy. Branching ratios for the prominent fragment ions are reported up to an ionization energy of I = 14 eV. It is shown that 1,2-epoxypropane cations initially formed with none or only little vibrational excitation in the electronic ground state do not dissociate, though their excess energy with respect to the lowest energetic fragmentation pathway is 1.25 eV. As the internal energy is increased, slow fragmentation into several dissociation channels is observed. This is used to explain a comparably slow dissociation process observed in the case of acetone molecular ions initially excited to their electronic à state. CH₂C(OH)CH₃⁺ and/or CH₃CHCHOH⁺ are proposed as precursors for these low-rate unimolecular reactions.     

Aluminum avoids the central position in AlB9- and AlB10-: photoelectron spectroscopy and ab initio study

The structures and the electronic properties of two Al-doped boron clusters, AlB(9)(-) and AlB(10)(-), were investigated via joint photoelectron spectroscopy and high-level ab initio study. The photoelectron spectra of both anions are relatively broad and have no vibrational structure. The geometrical structures were established by unbiased global minimum searches using the Coalescence Kick method and comparison between the experimental and calculated vertical electron detachment energies. The results show that both clusters have quasi-planar structures and that the Al atom is located at the periphery. Chemical bonding analysis revealed that the global minimum structures of both anions can be described as doubly (σ- and π-) aromatic systems. The nona-coordinated wheel-type structure of AlB(9)(-) was found to be a relatively high-lying isomer, while a similar structure for the neutral AlB(9) cluster was previously shown to be either a global minimum or a low-lying isomer.     

Lithium intercalation of phenyl-capped aniline dimers: a study by photoelectron spectroscopy and quantum chemical calculations

Structural and electronic properties of pristine and lithium-intercalated, phenyl-capped aniline dimers as a model for the lithium-polyaniline system have been studied by photoelectron spectroscopy and quantum chemical calculations. It was found that the electronic structure of reduced and oxidized forms of oligoanilines is only weakly affected by isomerism. Upon intercalation, charge transfer from the Li-atoms is remarkable and highly localized at N-atomic sites, where configurations are energetically favored in which both N atoms of the dimers are bound to Li atoms. Conversion of nitrogen sites is different for the two forms of aniline dimers and incomplete up to high intercalation levels, indicating a pronounced role of solid-state effects in the formation of such compounds.     

Kinetics of the sulfur oxidation on palladium: a combined in situ x-ray photoelectron spectroscopy and density-functional study

We studied the reaction kinetics of sulfur oxidation on the Pd(100) surface by in situ high resolution x-ray photoelectron spectroscopy and ab initio density functional calculations. Isothermal oxidation experiments were performed between 400 and 500 K for small amounts (~0.02 ML) of preadsorbed sulfur, with oxygen in large excess. The main stable reaction intermediate found on the surface is SO(4), with SO(2) and SO(3) being only present in minor amounts. Density-functional calculations depict a reaction energy profile, which explains the sequential formation of SO(2), SO(3), and eventually SO(4), also highlighting that the in-plane formation of SO from S and O adatoms is the rate limiting step. From the experiments we determined the activation energy of the rate limiting step to be 85 ± 6 kJ mol(-1) by Arrhenius analysis, matching the calculated endothermicity of the SO formation.     

Laser-muon spin spectroscopy in liquids - a technique to study the excited state chemistry of transients

This study introduces laser-muon spin spectroscopy in the liquid phase, which extends muonium chemistry in liquids to the realm of excited states and enables the detection of muoniated molecules by their spin evolution after laser excitation. This leads to new opportunities to study the Kinetic Isotope Effects (KIEs) of muonium/atomic hydrogen reactions and to probe transient chemistry in radiolysis processes involved in muonium formation, as well as muoniated intermediates in excited states.     

Vibrationally resolved photoelectron spectroscopy of BO- and BO2-: a joint experimental and theoretical study

We report a photoelectron spectroscopy and computational study of two simple boron oxide species: BO- and BO2-. Vibrationally resolved photoelectron spectra are obtained at several photon energies (355, 266, 193, and 157 nm) for the 10B isotopomers, 10BO- and 10BO2-. In the spectra of 10BO-, we observe transitions to the 2Sigma+ ground state and the 2Pi excited state of 10BO at an excitation energy of 2.96 eV. The electron affinity of 10BO is measured to be 2.510+/-0.015 eV. The vibrational frequencies of the ground states of 10BO- and 10BO and the 2Pi excited state are measured to be 1725+/-40, 1935+/-30, and 1320+/-40 cm-1, respectively. For 10BO2-, we observe transitions to the 2Pig ground state and two excited states of 10BO2, 2Piu, and 2Sigmau+, at excitation energies of 2.26 and 3.04 eV, respectively. The electron affinity of 10BO2 is measured to be 4.46+/-0.03 eV and the symmetrical stretching vibrational frequency of the 2Piu excited state of 10BO2 is measured to be 980+/-30 cm-1. Both density functional and ab initio calculations are performed to elucidate the electronic structure and chemical bonding of the two boron oxide molecules. Comparisons with the isoelectronic AlO- and AlO2- species and the closely related molecules CO, N2, CN-, and CO2 are also discussed.     

Single base interrogation by a fluorescent nucleotide: each of the four DNA bases identified by fluorescence spectroscopy

Nucleoside C, which contains a rigid nitroxide spin label, is effectively reduced in DNA by sodium sulfide to the corresponding amine, yielding a fluorescent probe (Cf) that can report the identity of its base-pairing partner in duplex DNA.     

On the structure and desorption dynamics of DNA bases adsorbed on gold: a temperature-programmed study

The structure and desorption dynamics of mono- and multilayer samples of adenine, cytosine, guanine, and thymine on polycrystalline gold thin films are studied using temperature-programmed desorption-infrared reflection absorption spectroscopy (TPD-IRAS) and temperature-programmed desorption-mass spectroscopy (TPD-MS). It is shown that the pyrimidines, adenine and guanine, adsorb to gold in a complex manner and that both adhesive (adenine) and cohesive (guanine) interactions contribute the apparent binding energies to the substrate surface. Adenine displays at least two adsorption sites, including a high-energy site (210 degrees C, approximately 136 kJ/mol), wherein the molecule coordinates to the gold substrate via the NH2 group in an sp3-like, strongly perturbed, nonplanar configuration. The purines, cytosine and thymine, display a less complicated adsorption/desorption behavior. The desorption energy for cytosine (160 degrees C, approximately 122 kJ/mol) is similar to those obtained for adenine and guanine, but desorption occurs from a single site of dispersed, nonaggregated cytosine. Thymine desorbs also from a single site but at a significantly lower energy (100 degrees C, approximately 104 kJ/mol). Infrared data reveal that the monolayer architectures discussed herein are structurally very different from those observed for the bases in the bulk crystalline state. It is also evident that both pyrimidines and purines adsorb on gold with the plane of the molecule in a nonparallel orientation with respect to the substrate surface. The results of this work are discussed in the context of improving the understanding of the design of capturing oligonucleotides or DNA strands for bioanalytical applications, in particular, for gold nanoparticle-based assays.     

X-ray photoelectron spectroscopy of pyrrolidinium-based ionic liquids: cation-anion interactions and a comparison to imidazolium-based analogues

We investigate seven 1-alkyl-1-methylpyrrolidinium-based ionic liquids, [C(n)C(1)Pyrr][X], using X-ray photoelectron spectroscopy (XPS). The electronic environment for each element is analysed and a robust fitting model is developed for the C 1s region that applies to each of the ionic liquids studied. This model allows accurate charge correction and the determination of reliable and reproducible binding energies for each ionic liquid studied. The electronic interaction between the cation and anion is investigated for ionic liquids with one and also two anions. i.e., mixtures. Comparisons are made to imidazolium-based ionic liquids; in particular, a detailed comparison is made between [C(8)C(1)Pyrr][X] and [C(8)C(1)Im][X](-), where X(?) is common to both ionic liquids.