Excitonic coupling of RNA-templated merocyanine dimer studied by higher-order transient absorption spectroscopy.

We report the synthesis and spectroscopic analysis of RNA containing the barbituric acid merocyanine rBAM2 as a nucleobase surrogate. Incorporation into RNA strands by solid-phase synthesis leads to fluorescence enhancement compared to the free chromophore. In addition, linear absorption studies show the formation of an excitonically coupled H-type dimer in the hybridized duplex. Ultrafast third- and fifth-order transient absorption spectroscopy of this non-fluorescent dimer suggests immediate (sub-200 fs) exciton transfer and annihilation due to the proximity of the rBAM2 units.

Unveiling the Role of Hidden Isomers in Large Stokes Shift in mKeima: Harnessing pH-Sensitive Dual-Emission in Bioimaging.

Elucidating the origin of large Stokes shift (LSS) in certain fluorescent proteins absorbing in blue/blue-green and emitting in red/far-red has been quite illusive. Using a combination of spectroscopic measurements, corroborated by theoretical calculations, the presence of four distinct forms of the chromophore of the red fluorescent protein mKeima is confirmed, two of which are found to be emissive: a feeble bluish-green fluorescence (∼520 nm), which is enhanced appreciably in a low pH or deuterated medium but significantly at cryogenic temperatures, and a strong emission in red (∼615 nm). Using femtosecond transient absorption spectroscopy, the trans-protonated form is found to isomerize within hundreds of femtoseconds to the cis-protonated form, which further yields the cis-deprotonated form within picoseconds followed by structural reorganization of the local environment of the chromophore. Thus, the mechanism of LSS is substantiated to proceed via stepwise excited-state isomerization followed by proton transfer involving three isomers, leaving the fourth one (trans-deprotonated) as a bystander. The exquisite pH sensitivity of the dual emission is further exploited in fluorescence microscopy.

Fluorescence-Detected Two-Quantum Photon Echoes via Cogwheel Phase Cycling.

Two-dimensional (2D) electronic spectroscopy can separate homogeneous and inhomogeneous broadening. While established methods usually probe a photon-echo signal, i.e., a third-order response, to access the homogeneous line width of singly excited states, the homogeneous line width of doubly excited states remained spectroscopically inaccessible. Here we demonstrate the acquisition of two-quantum (2Q) photon echoes using fluorescence-detected 2D spectroscopy. In these eighth-order signals, 2Q coherences are rephased with themselves, leading to line-narrowed 2Q-2Q 2D spectra. By using cogwheel phase cycling, adapted from nuclear magnetic resonance spectroscopy, we isolate the 2Q-2Q 2D spectra of a squaraine dimer and a squaraine polymer and verify the same selectivity of cogwheel phase cycling compared to traditional "nested" phase cycling. The observed difference, between the two systems, in the homogeneous line width of the biexciton can be rationalized as a signature of the interplay of exciton-exciton annihilation, exciton diffusion, and exciton delocalization.

A Revisit on Impulsive Stimulated Raman Spectroscopy: Importance of Spectral Dispersion of Chirped Broadband Probe.

The usefulness of a chirped broadband probe and spectral dispersion to obtain Raman spectra under nonresonant/resonant impulsive excitation is revisited. A general methodology is presented that inherently takes care of phasing the time-domain low-frequency oscillations without probe pulse compression and retrieves the absolute phase of the oscillations. As test beds, neat solvents (CCl4, CHCl3, and CH2Cl2) are used. Observation of periodic intensity modulation along detection wavelengths for particular modes is explained using a simple electric field interaction picture. This method is extended to diatomic molecule (iodine) and polyatomic molecules (Nile blue and methylene blue) to assign vibrational frequencies in ground/excited electronic state that are supported by density functional theory calculations. A comparison between frequency-domain and time-domain counterparts, i.e., stimulated Raman scattering and impulsive stimulated Raman scattering using degenerate pump-probe pairs is presented, and most importantly, it is shown how impulsive stimulated Raman scattering using chirped broadband probe retains unique advantages offered by both.

On the electronically nonadiabatic decomposition dynamics of furazan and triazole energetic molecules.

The combined results of ab initio electronic-structure calculations, nonadiabatic molecular dynamics simulations using ab initio multiple spawning, and previous spectroscopic investigations of jet-cooled molecules provide strong evidence of a (π,σ*)-mediated decomposition mechanism for the furazan and triazole energetic molecules. The importance of dissociative excited states formed by electron promotion from a π molecular orbital to a σ* molecular orbital is explored for the furazan and triazole energetic molecules. Dissociative (π,σ*) states of furazan and triazole energetic molecules can be populated by nonadiabatic surface jump from the (π,π*) or the (n,π*) state. Finally, conical intersections between (π,σ*) potential energy surfaces (PESs) and the ground PES influence the eventual fragmentation dynamics of the furazan and triazole energetic molecules. Due to structural similarity of the triazole molecule with the pyrrole molecule, a comparison of nonadiabatic dynamics of these two molecules is also presented. The N-N bond dissociation is found to be a barrierless pathway for the triazole molecule, whereas the N-H bond dissociation exhibits a barrierless pathway for the pyrrole molecule. The present work, thus, provides insights into the excited-state chemistry of furazan and triazole energetic functional groups. The same insight can also be relevant for other energetic molecules.