An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We have synthesized a series of compounds comprising the halide-free cadmium chalcogenide cluster dianions [Cd8Se(SePh)(16)](2-), [Cd17Se4(SePh)(28)](2-), [Cd17S4(SPh)(28)](2-), and [Cd17Se4(SPh)(28)](2-) to study their size- and composition-dependent electronic properties free of matrix effects. Toward this end, photoelectron spectra of the isolated dianions electrosprayed from solution were recorded at several detachment photon energies. Together with quantum chemical calculations, these data reveal a systematic correlation between electronic properties such as electron affinities or repulsive Coulomb barriers and the composition/size of these semiconducting cluster complexes. We infer that the excess negative charges are localized at the apical sites of these near-tetrahedral molecules.

Fractionation according to ion mobility and mass-to-charge ratio has been used to select individual isomers of deprotonated DNA oligonucleotide multianions for subsequent isomer-resolved photoelectron spectroscopy (PES) in the gas phase. Isomer-resolved PE spectra have been recorded for tetranucleotides, pentanucleotides, and hexanucleotides. These were studied primarily in their highest accessible negative charge states (3-, 4-, and 5-, respectively), as provided by electrospraying from room temperature solutions. In particular, the PE spectra obtained for pentanucleotide tetraanions show evidence for two coexisting classes of gas-phase isomeric structures. We suggest that these two classes comprise: (i) species with excess electrons localized exclusively at deprotonated phosphate backbone sites and (ii) species with at least one deprotonated base (in addition to several deprotonated phosphates). By permuting the sequence of bases in various [A(5-x)T(x)](4-) and [GT(4)](4-) pentanucleotides, we have established that the second type of isomer is most likely to occur if the deprotonated base is located at the first or last position in the sequence. We have used a combination of molecular mechanics and semiempirical calculations together with a simple electrostatic model to explore the photodetachment mechanism underlying our photoelectron spectra. Comparison of predicted to measured photoelectron spectra suggests that a significant fraction of the detected electrons originates from the DNA bases (both deprotonated and neutral).

We have developed a novel instrument that combines ion mobility spectrometry, mass spectrometry, and photoelectron spectroscopy. The instrument couples an electrospray ion source, a high transmission ion mobility cell based on ion funnels, a quadrupole mass filter, and a time-of-flight (magnetic bottle) photoelectron spectrometer operated with a pulsed detachment laser. We show that the instrument can resolve highly structured anion arrival time distributions and at the same time provide corresponding photoelectron spectra-using the DNA oligonucleotide ion [dC(6) - 5H](5-) as a test case. For this multianion we find at least four different, noninterconverting isomers (conformers) simultaneously present in the gas phase at room temperature. For each of these we record well-resolved and remarkably different photoelectron spectra at each of three different detachment laser wavelengths. Two-dimensional ion mobility/electron binding energy plots can be acquired with an automated data collection procedure. We expect that this kind of instrument will significantly improve the capabilities for structure determination of (bio)molecular anions in the gas phase.

Abstract The ultrafast response of singly negatively charged C60 fullerene in solution has been investigated by femtosecond pump-probe absorption spectroscopy and transient anisotropy in the visible and near-infrared region. Pump excitation within the near-infrared band demonstrates that this spectral feature can be described as a vibrational progression associated with a single electronic transition. Relaxation of the first electronically excited state occurs primarily by internal conversion with a time constant of 3 ps, slightly depending on the solvents, tetrahydrofuran or o-dichlorobenzene, and also on the excitation wavelength. An excitation of the second electronically excited state around 530 nm leads to an ultrafast internal conversion to the first excited state with a pulse-limited time constant of less than 100 fs. As a minor channel, stimulated emission in the spectral regime of 1150–1300 nm was observed from the first electronically excited state both after near-infrared and visible excitation. After internal conversion to the electronic ground state, C60− dissipates its excess internal energy into the solvent on a longer timescale of 40–70 ps. The transient anisotropy associated with directly populating the first excited state reveals an ultrafast component decaying within 100 fs, which is attributed to ultrafast vibrational motions, conceivably arising from excited state pseudorotation.

We have recorded the first conformer-selective photoelectron spectra of a protein polyanion in the gas-phase. Bovine cytochrome c protein was studied in 8 different negative charge states ranging from 5- to 12-. Electron binding energies were extracted for all charge states and used as a direct probe of intramolecular Coulomb repulsion. Comparison of experimental results with simulations shows that the experimental outcome can be reproduced with a simple electrostatic model. Energetics are consistent with a structural transition from a folded to an unfolded conformational state of the protein as the number of charges increases. Furthermore, the additional ion-mobility data show that the onset of unfolding can be assigned to charge state 6- where three conformers can be distinguished.

Excited state dynamics of acetonitrile cluster anions, (CH3CN)n-, were investigated using time-resolved photoelectron imaging (TRPEI) for 20⩽n⩽50. The clusters were excited and then photodetached with femtosecond pump and probe pulses at 790 and 395nm, respectively. Excited state lifetimes varied between 200 and 270fs over this size range, showing no obvious size trend. Experimental evidence indicates that we are exciting ‘isomer II’ clusters in which the excess electron is valence-bound to a solvated anionic dimer core. The absence of an obvious size-dependence in the excited state lifetimes is consistent with such a structure.

We have used femtosecond time-resolved photoelectron spectroscopy to examine the photodissociation dynamics of doubly charged anions IrBr62− after excitation at hνpump=1.6 eV and with a detachment photon energy of hνprobe=4.8 eV. Excited state dynamics proceed by successive decay of the initially excited state, by way of an intermediate and back to the electronic ground state. This is associated with lifetimes of τ1=2.1±0.3 ps and τ2=21±2 ps, respectively. After nonadiabatic relaxation, the internal energy of the dianion is sufficiently large to induce fragmentation and delayed emission of Br− over the repulsive Coulomb barrier with a 79±21 ps time constant. As both fragments are negatively charged, Coulomb repulsion at early times (and correspondingly small separations) is reflected in the transient photoelectron spectra. Analysis of both shifts and intensities of the time-dependent bromide detachment features allows determination of the shape of the dissociation barrier. A lower limit of the outer height was retrieved from the kinetic energy release of KER≥1.6 eV. Modeling of the dissociation rate with statistical rate theory results in an inner barrier height of ERCB=0.95 eV.

We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

Using femtosecond time-resolved photoelectron imaging, electron-hole pairs are created in size-selected Hg(n)(-) anion clusters (n=9-20), and the subsequent decay dynamics are measured. These clusters eject electrons via Auger decay on time scales of 100-600 fs. There is an abrupt increase in the Auger decay time for clusters larger than Hg(12)(-), coinciding with the onset of the transition from van der Waals to covalent bonding in mercury clusters. Our results also show evidence for subpicosecond excited state relaxation attributed to inelastic electron-electron and electron-hole scattering as well as hole-induced contraction of the cluster.

Electronic relaxation dynamics subsequent to s --> p excitation of the excess electron in large anionic water clusters, (H(2)O)(n)(-) and (D(2)O)(n)(-) with 25 < or = n < or = 200, were investigated using time-resolved photoelectron imaging. Experimental improvements have enabled considerably larger clusters to be probed than in previous work, and the temporal resolution of the instrument has been improved. New trends are seen in the size-dependent p-state lifetimes for clusters with n > or = 70, suggesting a significant change in the electron-water interaction for clusters in this size range. Extrapolating the results for these larger clusters to the infinite-size limit yields internal conversion lifetimes tau(IC) of 60 and 160 fs for electrons dissolved in H(2)O and D(2)O, respectively. In addition, the time-evolving spectra show evidence for solvent relaxation in the excited electronic state prior to internal conversion and in the ground state subsequent to internal conversion. Relaxation in the excited state appears to occur on a time scale similar to that of internal conversion, while ground state solvent dynamics occur on a approximately 1 ps time scale, in reasonable agreement with previous measurements on water cluster anions and electrons solvated in liquid water.

Solvated electrons, and hydrated electrons in particular, are important species in condensed phase chemistry, physics, and biology. Many studies have examined the formation mechanism, reactivity, spectroscopy, and dynamics of electrons in aqueous solution and other solvents, leading to a fundamental understanding of the electron-solvent interaction. However, key aspects of solvated electrons remain controversial, and the interaction between hydrated electrons and water is of central interest. For example, although researchers generally accept that hydrated electrons, eaq-, occupy solvent cavities, another picture suggests that the electron resides in a diffuse orbital localized on a H3O radical. In addition, researchers have proposed two physically distinct models for the relaxation mechanism when the electron is excited. These models, formulated to interpret condensed phase experiments, have markedly different timescales for the internal conversion from the excited p state to the ground s state.Studies of negatively charged clusters, such as (H2O)n- and I-(H2O)n, offer a complementary perspective for studying aqueous electron solvation. In this Account, we use time-resolved photoelectron spectroscopy (TRPES), a femtosecond pump-probe technique in which mass-selected anions are electronically excited and then photodetached at a series of delay times, to focus on time-resolved dynamics in these and similar species. In (H2O)n-,TRPES gives evidence for ultrafast internal conversion in clusters up to n=100. Extrapolation of these results yields a p-state lifetime of 50 fs in the bulk limit. This is in good agreement with the nonadiabatic solvation model, one of the models proposed for relaxation of eaq-. Similarly, experiments on (MeOH)n- up to n=450 give an extrapolated p-state lifetime of 150fs. TRPES investigations of I-(H2O)n and I-(CH3CN)n probe a different aspect of electron solvation dynamics. In these experiments,an ultraviolet pump pulse excites the cluster analog of the charge-transfer-to-solvent (CTTS) band, ejecting an electron from the iodide into the solvent network. The probe pulse then monitors the solvent response to this excess electron,specifically its stabilization via solvent rearrangement. In I-(H2O)n, the iodide sits outside the solvent network, as does the excess electron initially formed by CTTS excitation. However, the iodide in I-(CH3CN)n is internally solvated, and both experimental and theoretical evidence indicate that electrons in (CH3CN)n- are internally solvated. Hence, these experiments reflect the complex dynamics that ensue when the electron is photo detached within a highly confined solvent cavity.

We have examined size-dependent electronic relaxation dynamics in isolated semiconducting mercury cluster anions using time-resolved photoelectron imaging. Relaxation following excitation from within the conduction (p-) band occurs on an ∼3–40 ps timescale and is attributed to non-adiabatic relaxation through the p-band. Exciting an electron from the valence (s-) band into the conduction band creates an electron–hole pair that relaxes prior to Auger emission. The dynamics associated with this feature occur on an ∼500 fs timescale and are attributed to either a hole-induced contraction of the cluster or electron–electron scattering.

We have used femtosecond time-resolved photoelectron spectroscopy to examine the photodissociation dynamics of doubly charged anions IrBr(6)(2-) after excitation at h nu(pump) = 1.6 eV and with a detachment photon energy of h nu(probe) = 4.8 eV. Excited state dynamics proceed by successive decay of the initially excited state, by way of an intermediate and back to the electronic ground state. This is associated with lifetimes of tau(1) = 2.1+/-0.3 ps and tau(2) = 21+/-2 ps, respectively. After nonadiabatic relaxation, the internal energy of the dianion is sufficiently large to induce fragmentation and delayed emission of Br(-) over the repulsive Coulomb barrier with a 79+/-21 ps time constant. As both fragments are negatively charged, Coulomb repulsion at early times (and correspondingly small separations) is reflected in the transient photoelectron spectra. Analysis of both shifts and intensities of the time-dependent bromide detachment features allows determination of the shape of the dissociation barrier. A lower limit of the outer height was retrieved from the kinetic energy release of KER > or = 1.6 eV. Modeling of the dissociation rate with statistical rate theory results in an inner barrier height of E(RCB) = 0.95 eV.

We present the first photoelectron (PE) spectra of polypeptide polyanions. Combining PE spectroscopy and mass spectrometry provides a direct measurement of the stability of the polyanions with respect to electron detachment and of the repulsive energy between excess charges. The second electron affinity of gramicidin was found to amount to 2.35 +/- 0.15 eV, and the value of the repulsive Coulomb barrier was estimated to be 0.5 +/- 0.15 eV. The spectra are interpreted as resulting from a competition between delayed and direct emission.

Electronic relaxation dynamics following interband excitation from the 6s to the 6p band in mass selected Hg13- clusters are measured through femtosecond time-resolved photoelectron imaging (TRPEI). This interband transition is pumped at 4.65eV and probed at 1.55eV. Auger decay of occurs on a timescale of 490±100fs, and a similar time constant is seen for the transient excited state population created by the pump pulse. These time constants are an order of magnitude faster than those seen in previous experiments in which the lone p-electron in Hg13- was excited within the p-band. The results presented here imply that substantial relaxation of either electrons in the p-band or the hole in the s-band takes place prior to Auger emission, with electron–electron scattering playing a key role in the fast observed dynamics.

Femtosecond time-resolved pump-probe photoelectron spectroscopy was used to study elementary relaxation processes occurring in isolated phthalocyanine-tetrasulfonate tetra-anions ([MPc(SO3)4]4-, M=Cu,Ni, and "free-base" [H2Pc(SO3)4]4-) following Q band excitation by one-photon absorption at 775 nm. Whereas the Cu and Ni systems decay rapidly by means of internal conversion without electron loss, the free-base phthalocyanine primarily undergoes excited state tunneling electron emission. This reflects less efficient coupling to lower lying states within the corresponding spin manifold. Results are interpreted in terms of (time-dependent) density functional theory calculations of ground and electronically excited states and kinetically modeled to yield the associated rates.

We have measured pump/probe photoelectron spectra of mass-selected, near room temperature C60- in the gas phase. The lifetime of the vibrationally excited B- (2Eg) state at a calculated energy of 1.26 eV was found to be tau = 2.2+/-0.2 ps. The dominant decay process corresponds to intramolecular radiationless transitions into ground state C60-. This is in contrast to C60 for which pumping at the absorption onset (1.95 eV) leads to predominantly intersystem crossing.