Zhengyang Zhang

Measuring the spectral diffusion of chlorophyll a using two-dimensional electronic spectroscopy.

Ultrafast two-dimensional electronic spectroscopy has been used to study the spectral diffusion of the Qy transition of chlorophyll a in methanol. The two time frequency-fluctuation correlation function (FFCF) of the transition has been measured using the center line slope method, together with optimized fitting of the linear spectrum. The FFCF was measured to decay over four time scales. The three fastest time constants of which were measured to be ∼65 fs, ∼0.5 ps, and ∼7 ps. These are assigned as the inertial component of solvation and spectrally diffusive solvation processes respectively. The fourth time constant (>1 ns) may be attributed to the chromophore structural inhomogeneity.

Purely absorptive fifth-order three-dimensional electronic spectroscopy

We demonstrate a method to measure a purely absorptive fifth-order three-dimensional (3D) electronic spectrum based on a pulse-shaper assisted pump-probe beam geometry setup. The 3D spectra are measured as a function of two independently controlled population times. With phase-cycling and data processing, purely absorptive 3D spectra of chlorophyll a are obtained.

Fifth-order three-dimensional electronic spectroscopy using a pump-probe configuration.

We present the theoretical details and experimental demonstration of fifth-order three-dimensional (3D) electronic spectroscopy using a pump-probe beam geometry. This is achieved using a pulse shaper and appropriate phase cycling schemes. We show how 8-step and 27-step phase cycling schemes can measure purely absorptive 3D spectra as well as 3D spectra for the individual fifth-order processes that contribute to the purely absorptive spectrum. 3D spectra as a function of two separate controllable waiting time periods can be obtained. The peak shapes and positions of the peaks in the experimental measurement correspond well to theory.

Long-Lived Radical Cations as Model Compounds for the Reactive One-Electron Oxidation Product of Vitamin E

Heterocyclic compounds with structures similar to vitamin E, but without the hydroxyl hydrogen atom, were synthesized and their electrochemical behavior examined in acetonitrile solutions and as solids in aqueous solutions of varying pH by attaching the compounds to the surface of a glassy carbon electrode. Compound 1, containing a fully methylated aromatic ring was found to be the most long-lived following one-electron oxidation, with its radical cation (1+*) surviving in acidic aqueous solutions and able to be isolated as a salt, 1+*(SbF6-), when reacted with NOSbF6 in CH3CN. Electrochemical, UV-vis and FTIR experiments on 1+*, in addition to the results from theoretical calculations, indicated that the electrochemical, electronic and structural properties of 1+* are very similar to those of the radical cation of vitamin E.

Direct observation of multistep energy transfer in LHCII with fifth-order 3D electronic spectroscopy

During photosynthesis, sunlight is efficiently captured by light-harvesting complexes, and the excitation energy is then funneled towards the reaction centre. These photosynthetic excitation energy transfer (EET) pathways are complex and proceed in a multistep fashion. Ultrafast two-dimensional electronic spectroscopy (2DES) is an important tool to study EET processes in photosynthetic complexes. However, the multistep EET processes can only be indirectly inferred by correlating different cross peaks from a series of 2DES spectra. Here we directly observe multistep EET processes in LHCII using ultrafast fifth-order three-dimensional electronic spectroscopy (3DES). We measure cross peaks in 3DES spectra of LHCII that directly indicate energy transfer from excitons in the chlorophyll b (Chl b) manifold to the low-energy level chlorophyll a (Chl a) via mid-level Chl a energy states. This new spectroscopic technique allows scientists to move a step towards mapping the complete complex EET processes in photosynthetic systems.

Ultrafast vibrational relaxation dynamics of carbonyl stretching modes in Os3(CO)12

The vibrational relaxation dynamics of the four infrared active carbonyl (CO) stretching normal modes of Os(3)(CO)(12) at 2068 cm(-1), 2034 cm(-1), 2014 cm(-1), and 2002 cm(-1) were measured using broad-band frequency resolved pump-probe spectroscopy. Transient absorption spectra of these modes were collected, and the fundamental, overtone, and combination bands were assigned. The frequency resolved pump-probe traces measured at the fundamental frequencies for the four stretching normal modes exhibited marked differences: the two axial modes at frequencies of 2068 cm(-1) and 2034 cm(-1) yielded similar bi-exponential decay traces, while the two equatorial modes at 2014 cm(-1) and 2002 cm(-1) showed a rising component, in addition to a bi-exponential decay. Due to the independence of the axial and equatorial stretching modes, it is shown that the axial-equatorial combination anharmonicity constants are near zero. This results in the appearance of the pump-probe signals of these combination bands at the same frequencies as the fundamental transitions, thus leading to interference and the resultant anomalous rising features. If unaccounted for, these interferences may lead to erroneous conclusions about the dynamics of these vibrational stretches. To avoid such pitfalls, it is therefore imperative to resolve such ambiguities. A corrected dynamical picture of the equatorial modes can be obtained by varying the center frequency of the pump pulse. The four modes have a slow vibrational excited population decay time of between 400 to 600 ps. We observe no obvious direct vibrational energy transfer between the axial and equatorial CO stretching modes.

Spectrally Resolved Super-Resolution Microscopy Unveils Multipath Reaction Pathways of Single Spiropyran Molecules

By recording both the images and emission spectra of thousands of single fluorescent molecules stochastically generated from the ring-opening reaction of a spiropyran, we provide mechanistic insights into its multipath reaction pathways. Through statistics of the measured single-molecule spectra, we identify two spectrally distinct isomers, presumably TTC and TTT cis-trans isomers, for the open-ring merocyanine product, and discover a strong solvent polarity-dependence for the relative population of the two isomers. From single-molecule spectral time traces, we further examine isomerization between the two product merocyanine isomers, as well as their ring-closure reaction back to the spiropyran form.

Generation and measurement of polarization shaped pulse trains in the ultraviolet

We demonstrate the generation and measurement of amplitude, phase and polarization shaped pulse trains tunable in the ultraviolet (UV) by means of sum-frequency generation and with interferometric phase stability.