Umesh Kadhane

A new technique for time-resolved daughter ion mass spectrometry on the microsecond to millisecond time scale using an electrostatic ion storage ring

A new method for time-resolved daughter ion mass spectrometry is presented, based on the electrostatic ion storage ring in Aarhus, ELISA. Ions with high internal energy, e.g., as a result of photoexcitation, dissociate and the yield of neutrals is monitored as a function of time. This gives information on lifetimes in the microsecond to millisecond time range but no information on the fragment masses. To determine the dissociation channels, we have introduced pulsed supplies with switching times of a few microseconds. This allows rapid switching from storage of parent ions to storage of daughter ions, which are dumped into a detector after a number of revolutions in the ring. A fragment mass spectrum is obtained by monitoring the daughter ion signal as a function of the ring voltages. This technique allows identification of the dissociation channels and determination of the time dependent competition between these channels.

Dianions of 7,7,8,8-tetracyano-p-quinodimethane and perfluorinated tetracyanoquinodimethane: Information on excited states from lifetime measurements in an electrostatic storage ring and optical absorption spectroscopy

We have developed an experimental technique that allows us to study the physics of short lived molecular dianions in the gas phase. It is based on the formation of monoanions via electrospray ionization, acceleration of these ions to keV energies, and subsequent electron capture in a sodium vapor cell. The dianions are stored in an electrostatic ion storage ring in which they circulate with revolution times on the order of 100 micros. This enables lifetime studies in a time regime covering five orders of magnitude, 10(-5)-1 s. We have produced dianions of 7,7,8,8-tetracyano-p-quinodimethane and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane (TCNQ-F(4)) and measured their lifetimes with respect to electron autodetachment. Our data indicate that most of the dianions were initially formed in electronically excited states in the electron transfer process. Two levels of excitation were identified by spectroscopy on the dianion of TCNQ-F(4), and the absorption spectrum was compared with spectra obtained from spectroelectrochemistry of TCNQ-F(4) in acetonitrile solution.

A Soret marker band for four-coordinate ferric heme proteins from absorption spectra of isolated Fe(III)-Heme+ and Fe(III)-Heme+(His) ions in vacuo.

In this work, we report the absorption spectra in the Soret band region of isolated Fe(III)-heme+ and Fe(III)-heme+(His) ions in vacuo from action spectroscopy. Fe(III)-heme+ refers to iron(III) coordinated by the dianion of protoporphyrin IX. We find that the absorption of the five-coordinate complex is similar to that of pentacoordinate metmyoglobin variants with hydrophobic binding pockets except for an overall blueshift of about 16 nm. In the case of four-coordinate iron(III), the Soret band is similar to that of five-coordinate iron(III) but much narrower. These spectra serve as a benchmark for theoretical modeling and also serve to identify the coordination state of ferric heme proteins. To our knowledge this is the first unequivocal spectroscopic characterization of isolated 4c ferric heme in the gas phase.

Photodissociation of isolated ferric heme and heme-His cations in an electrostatic ion storage ring.

Photodissociation of isolated Fe(III)-heme(+) and Fe(III)-heme(+)(His) ions in the gas phase has been investigated using an electrostatic storage ring. The experiment provides three pieces of information, namely fragmentation channels, dissociation times, and absorption spectra. After photoexcitation with either 390 or 532 nm light, we find that the fragmentation takes place on a microsecond to millisecond time scale, and the channels are CH(2)COOH loss (beta-cleavage reaction) and histidine loss from Fe(III)-heme(+) and Fe(III)-heme(+)(His), respectively. These channels were also observed by means of collision-induced dissociation. Significant information on the nonradiative processes that occur after photoexcitation was revealed from the decay spectra. At early times (first two to three milliseconds), the decay of the photoexcited ions is well-described by a statistical model based on an Arrhenius-type expression for the rate constant. The activation energy and preexponential factor are 1.9 +/- 0.2 eV and 1 x 10(17) to 1 x 10(21) s(-1) for heme(+) and 1.4 +/- 0.2 eV and 1 x 10(16) to 1 x 10(19) s(-1) for heme(+)(His). Decay on a longer time scale was also observed and is ascribed to the population of lower-lying states with higher spin multiplicity because intersystem crossing back to the electronic ground-state is a bottleneck for the dissociation. The measurements give lifetimes for these lower-lying states of about 10 ms after 390 nm excitation and we estimate the probability of spin flip to be 0.3 and 0.8 for heme(+) and heme(+)(His), respectively.

Near-infrared photoabsorption by C 60 dianions in a storage ring

We present a detailed study of the electronic structure and the stability of C(60) dianions in the gas phase. Monoanions were extracted from a plasma source and converted to dianions by electron transfer in a Na vapor cell. The dianions were then stored in an electrostatic ring, and their near-infrared absorption spectrum was measured by observation of laser induced electron detachment. From the time dependence of the detachment after photon absorption, we conclude that the reaction has contributions from both direct electron tunneling to the continuum and vibrationally assisted tunneling after internal conversion. This implies that the height of the Coulomb barrier confining the attached electrons is at least approximately 1.5 eV. For C(60)(2-) ions in solution electron spin resonance measurements have indicated a singlet ground state, and from the similarity of the absorption spectra we conclude that also the ground state of isolated C(60)(2-) ions is singlet. The observed spectrum corresponds to an electronic transition from a t(1u) lowest unoccupied molecular orbital (LUMO) of C(60) to the t(1g) LUMO+1 level. The electronic levels of the dianion are split due to Jahn-Teller coupling to quadrupole deformations of the molecule, and a main absorption band at 10,723 cm(-1) corresponds to a transition between the Jahn-Teller ground states. Also transitions from pseudorotational states with 200 cm(-1) and (probably) 420 cm(-1) excitation are observed. We argue that a very broad absorption band from about 11,500 cm(-1) to 13,500 cm(-1) consists of transitions to so-called cone states, which are Jahn-Teller states on a higher potential-energy surface, stabilized by a pseudorotational angular momentum barrier. A previously observed, high-lying absorption band for C(60)(-) may also be a transition to a cone state.

Photodissociation of protonated tryptophan and alteration of dissociation pathways by complexation with crown ether

The behavior of protonated tryptophan (TrpH(+)) and its complex with 18-crown-6-ether (CE) after photoexcitation has been explored based on measurements of dissociation lifetimes, fragmentation channels, and absorption spectra using an electrostatic ion storage ring. A recent implementation of pulsed power supplies for the ring elements with microsecond response times allows us to identify the daughter ion fragment masses and to disentangle fragmentation that occurs from excited states immediately after photoexcitation from that occurring on a longer time scale of several microseconds to milliseconds. We find that attachment of crown ether significantly alters the dissociation channels since it renders the pisigma(*)(NH(3)) state inaccessible and hence prevents the N-H bond breakage which is an important fragmentation channel of TrpH(+). As a result, on a long time scale (>10 micros), photoexcited TrpH(+)(CE) decays exponentially whereas TrpH(+) displays a power-law decay. The only ions remaining in the latter case are Trp(+) radical cations with a broad internal energy distribution caused by the departing hydrogen. Large changes in the fragment branching ratios as functions of excitation wavelength between 210 and 290 nm were found for both TrpH(+) and TrpH(+)(CE).

Electron‐Capture‐Induced Dissociation of Microsolvated Di‐ and Tripeptide Monocations: Elucidation of Fragmentation Channels from Measurements of Negative Ions

The results from an experimental study of bare and microsolvated peptide monocations in high-energy collisions with cesium vapor are reported. Neutral radicals form after electron capture from cesium, which decay by H loss, NH(3) loss, or N-C(alpha) bond cleavage into characteristic z(*) and c fragments. The neutral fragments are converted into negatively charged species in a second collision with cesium and are identified by means of mass spectrometry. For protonated GA (G = glycine, A = alanine), the branching ratio between NH(3) loss and N-C(alpha) bond cleavage is found to strongly depend on the molecule attached (H(2)O, CH(3)CN, CH(3)OH, and 18-crown-6 ether (CE)). Addition of H(2)O and CH(3)OH increases this ratio whereas CH(3)CN and CE decrease it. For protonated AAA ([AAA+H](+)), a similar effect is observed with methanol, while the ratio between the z(1) and z(2) fragment peaks remains unchanged for the bare and microsolvated species. Density functional theory calculations reveal that in the case of [GA+H](+)(CE), the singly occupied molecular orbital is located mainly on the amide group in accordance with the experimental results.

Experimental study of K-shell ionization of low-Z solids in collisions with intermediate-velocity carbon ions and the local plasma approximation

K-shell vacancy production in low-atomic-number (Z t = 17–29) solid targets ha sb een measured in collisions of highly charged carbon ions with energies of 1.5–6 MeV u −1 .T he K-shel li onization cross sections of Cl, K, Ti, Fe and Cu are derived from the measured K x-ray cross sections. The present data-set has been used to test the predictions of a theoretical model based on the local plasma approximation (LPA). This theory takes into account the response of solid core electrons working within the dielectric formalism. We find that this ab initio ion–solid model gives very good agreement with the measured data for Fe and Cu targets, while it tends to under-estimate the data for the most symmetric collision systems studied here. We discuss the range of validity of the LPA in terms of the symmetry parameter and the impact velocity. On the other hand, am odel based on the perturbed stationary state approximation, designed for ion–atom collisions (ECPSSR) is found to give excellent agreement with the measured data for all target elements over the whole energy range. All the measured cross sections for different targets are found to follow a universal scaling rule predicted by the ECPSSR.

Effect of multiple plasmon excitation on single, double and multiple ionizations of C60 in collisions with fast highly charged Si ions

We have investigated the single and multiple ionizations of the C60 molecule in collisions with fast Siq+ projectiles for various projectile charge states (q) between q = 6 and 14. The q-dependence of the ionization cross sections and their ratios is compared with the giant dipole plasmon resonance (GDPR) model. The excellent qualitative agreement with the model in case of single and double ionizations and also a reasonable agreement with the triple (and to some extent with quadruple) ionization (without evaporation) yields signify dominant contributions of the single-, double- and triple-plasmon excitations on the single- and multiple-ionization process.

Valence Shell Photoelectron Spectroscopy of Pyrene and Fluorene: Photon Energy Dependence in the Far-Ultraviolet Region

Inner and outer valence photoelectron spectra (PES) of pyrene and fluorene, two members of the polycyclic aromatic hydrocarbon (PAH) family, were recorded with a high-resolution synchrotron photoelectron spectrometer. Relative photoelectron emission cross sections were measured at photon energies between 15 and 40 eV. Several bands observed in the experimental PES were assigned with the help of OVGF/cc-pVDZ calculations. The first ionization potentials were estimated to be 7.436 ± 0.015 and 7.944 ± 0.055 eV for pyrene and fluorene, respectively. Photoelectron emission cross sections show a clear difference in trend for inner (σ-dominated) and outer (π-dominated) bands. Contrary to the expectation from the trend observed in benzene, the inner bands significantly dominate in the photon energy region from 15 to 27 eV and then are found to contribute uniformly. A pronounced peak in the cross sections is observed at a photon energy of approximately 17 eV for both molecules (irrespective of the difference in symmetry and structure), particularly for the inner valence bands. The feature is observed to be independent of the details of the molecular orbital associated with the outgoing electron. These observations are correlated to a collective excitation in the far-ultraviolet region.