Jyoti Rajput

Gas Phase Absorption Studies of Photoactive Yellow Protein Chromophore Derivatives

Photoabsorption spectra of deprotonated trans p-coumaric acid and two of its methyl substituted derivatives have been studied in gas phase both experimentally and theoretically. We have focused on the spectroscopic effect of the location of the two possible deprotonation sites on the trans p-coumaric acid which originate to either a phenoxide or a carboxylate. Surprisingly, the three chromophores were found to have the same absorption maximum at 430 nm, in spite of having different deprotonation positions. However, the absorption of the chromophore in polar solution is substantially different for the distinct deprotonation locations. We also report on the time scales and pathways of relaxation after photoexcitation for the three photoactive yellow protein chromophore derivatives. As a result of these experiments, we could detect the phenoxide isomer within the deprotonated trans p-coumaric acid in gas phase; however, the occurrence of the carboxylate is uncertain. Several computational methods were used simultaneously to provide insights and assistance in the interpretation of our experimental results. The calculated excitation energies S(0)-S(1) are in good agreement with experiment for those systems having a negative charge on a phenoxide moiety. Although our augmented multiconfigurational quasidegenerate perturbation theory calculations agree with experiment in the description of the absorption spectrum of anions with a carboxylate functional group, there are some puzzling disagreements between experiment and some calculational methods in the description of these systems.

UV excited-state photoresponse of biochromophore negative ions.

Members of the green fluorescent protein (GFP) family may undergo irreversible phototransformation upon irradiation with UV light. This provides clear evidence for the importance of the higher-energy photophysics of the chromophore, which remains essentially unexplored. By using time-resolved action and photoelectron spectroscopy together with high-level electronic structure theory, we directly probe and identify higher electronically excited singlet states of the isolated para- and meta-chromophore anions of GFP. These molecular resonances are found to serve as a doorway for very efficient electron detachment in the gas phase. Inside the protein, this band is found to be resonant with the quasicontinuum of a solvated electron, thus enhancing electron transfer from the GFP to the solvent. This suggests a photophysical pathway for photoconversion of the protein, where GFP resonant photooxidation in solution triggers radical redox reactions inside these proteins.

Photodissociation pathways and lifetimes of protonated peptides and their dimers

Photodissociation lifetimes and fragment channels of gas-phase, protonated YA(n) (n = 1,2) peptides and their dimers were measured with 266 nm photons. The protonated monomers were found to have a fast dissociation channel with an exponential lifetime of ~200 ns while the protonated dimers show an additional slow dissociation component with a lifetime of ~2 μs. Laser power dependence measurements enabled us to ascribe the fast channel in the monomer and the slow channel in the dimer to a one-photon process, whereas the fast dimer channel is from a two-photon process. The slow (1 photon) dissociation channel in the dimer was found to result in cleavage of the H-bonds after energy transfer through these H-bonds. In general, the dissociation of these protonated peptides is non-prompt and the decay time was found to increase with the size of the peptides. Quantum RRKM calculations of the microcanonical rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system, estimated separately on the basis of the equipartition theorem. It demonstrates encouraging results in predicting fragmentation lifetimes of protonated peptides. Finally, we present the first experimental evidence for a photo-induced conversion of tyrosine-containing peptides into monocyclic aromatic hydrocarbon along with a formamide molecule both found in space.

An electrostatic deceleration lens for highly charged ions

The design and implementation of a purely electrostatic deceleration lens used to obtain beams of highly charged ions at very low energies is presented. The design of the lens is such that it can be used with parallel as well as diverging incoming beams and delivers a well focused low energy beam at the target. In addition, tuning of the final energy of the beam over a wide range (1 eV/q to several hundred eV/q, where q is the beam charge state) is possible without any change in hardware configuration. The deceleration lens was tested with Ar(8+), extracted from an electron cyclotron resonance ion source, having an initial energy of 30 keV/q and final energies as low as 70 eV/q have been achieved.

Native Frames: Disentangling Sequential from Concerted Three-Body Fragmentation

A key question concerning the three-body fragmentation of polyatomic molecules is the distinction of sequential and concerted mechanisms, i.e., the stepwise or simultaneous cleavage of bonds. Using laser-driven fragmentation of OCS into O^{+}+C^{+}+S^{+} and employing coincidence momentum imaging, we demonstrate a novel method that enables the clear separation of sequential and concerted breakup. The separation is accomplished by analyzing the three-body fragmentation in the native frame associated with each step and taking advantage of the rotation of the intermediate molecular fragment, CO^{2+} or CS^{2+}, before its unimolecular dissociation. This native-frame method works for any projectile (electrons, ions, or photons), provides details on each step of the sequential breakup, and enables the retrieval of the relevant spectra for sequential and concerted breakup separately. Specifically, this allows the determination of the branching ratio of all these processes in OCS^{3+} breakup. Moreover, we find that the first step of sequential breakup is tightly aligned along the laser polarization and identify the likely electronic states of the intermediate dication that undergo unimolecular dissociation in the second step. Finally, the separated concerted breakup spectra show clearly that the central carbon atom is preferentially ejected perpendicular to the laser field.

Communication: Atomic and molecular Rydbergs from water

We report the formation of energetic neutral Rydberg hydrogen atoms and transient Rydberg molecular ions, [(H(2)O)(q+)](⋆) in ion-impact dissociation of isolated water molecules. The kinetic energy spectra of the neutral Rydberg H atoms are determined from the complete study of (H(⋆), H(+), O(+)) dissociation channel. This channel of water dissociation is suggested as a possible additional source of the energetic neutrals detected in upper atmospheres of extra solar planets, and of slow electrons which are known to play a major role in radiation induced damage to living cells.

Three-body dissociation of OCS3+: Separating sequential and concerted pathways

Events from the sequential and concerted modes of the fragmentation of OCS3+ that result in coincident detection of fragments C+, O+, and S+ have been separated using a newly proposed representation. An ion beam of 1.8 MeV Xe9+ is used to make the triply charged molecular ion, with the fragments being detected by a recoil ion momentum spectrometer. By separating events belonging exclusively to the sequential mode of breakup, the electronic states of the intermediate molecular ion (CO2+ or CS2+) involved are determined, and from the kinetic energy release spectra, it is shown that the low lying excited states of the parent OCS3+ are responsible for this mechanism. An estimate of branching ratios of events coming from sequential versus concerted mode is presented.

Three-body dissociation of OCS3+ : separating sequential and concerted pathways

Three body fragmentation pathways of OCS3+ molecular ion leading to detection of C + + O + + S + in coincidence have been studied using the technique of recoil ion momentum spectroscopy. This fragmentation can occur either via a one step concerted process or a two step sequential process. In the first step of the sequential pathway either CO2+ or CS2+ is formed. By separating the events coming from the two processes, branching ratios are determined and the possible electronic states associated with the intermediate CO2+ or CS2+ have been identified.

Angular distributions in two body breakup of OCSq+ ions

The angular distribution of the correlated dissociation fragments with respect to the beam direction has been topic of interest for both experimentalists and theoreticians. This is of fundamental importance in various areas of science and technology (see, e.g. [1]). In the past decades, many experimental methods have been used to study the anisotropy in the angular distributions of fragments of multiply ionized molecules formed by impact of highly charged ion (e.g. [2] and references therein).

Orientation and alignment effects in ion-induced fragmentation of isolated water molecules

We report the angular distribution of the fragment ions formed in the collision of Xe9+ ions with isolated water molecules. A significant anisotropy, and strong alignment effects have been seen. It is observed that there is a strong forward - backward asymmetry in the emission of protons and oxygen ions in the three body dissociation of multiply charged water molecules.