Proton transfer reaction plays an essential role in a myriad of chemical and biological processes, and to reveal the choreography of the proton motion intra- and intermolecularly, a spectroscopic technique capable of capturing molecular structural snapshots on the intrinsic time scale of proton transfer motions is needed. The photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) serves as a paradigm case to dissect excited state proton transfer (ESPT) events in aqueous solution, triggered precisely by photoexcitation. We have used femtosecond stimulated Raman spectroscopy (FSRS) to yield novel insights into the ultrafast conformational dynamics of photoexcited HPTS in complex with water and acetate molecules. Marker bands attributed to the deprotonated form of HPTS (1139 cm(-1), ∼220 fs rise) appear earlier and faster than the monomer acetic acid peak (864 cm(-1), ∼530 fs rise), indicating that water molecules actively participate in the ESPT chain. Several key low-frequency modes at 106, 150, 195, and 321 cm(-1) have been identified to facilitate ESPT at different stages from 300 fs, 1 ps, to 6 ps and beyond, having distinctive dynamics contributing through hydrogen bonds with 0, 1, and more intervening water molecules. The time-resolved FSRS spectroscopy renders a direct approach to observe the reactive coupling between the vibrational degrees of freedom of photoexcited HPTS in action, therefore revealing the anharmonicity matrix both within HPTS and between HPTS and the neighboring acceptor molecules. The observed excited state conformational dynamics are along the ESPT multidimensional reaction coordinate and are responsible for the photoacidity of HPTS in aqueous solution.

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To understand chemical reactivity of molecules in condensed phase in real time, a structural dynamics technique capable of monitoring molecular conformational motions on their intrinsic time scales, typically on femtoseconds to picoseconds, is needed. We have studied a strong photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS, pK(a)* ≈ 0) in pure methanol and observed that excited-state proton transfer (ESPT) is absent, in sharp contrast with our previous work on HPTS in aqueous solutions wherein ESPT prevails following photoexcitation. Two transient vibrational marker bands at ~1477 (1454) and 1532 (1528) cm(-1) appear in CH3OH (CD3OD), respectively, rising within the instrument response time of ~140 fs and decaying with 390-470 (490-1400) fs and ~200 ps time constants in CH3OH (CD3OD). We attribute the mode onset to small-scale coherent proton motion along the pre-existing H-bonding chain between HPTS and methanol, and the two decay stages to the low-frequency skeletal motion-modulated Franck-Condon relaxation within ~1 ps and subsequent rotational diffusion of H-bonding partners in solution before fluorescence. The early time kinetic isotope effect (KIE) of ~3 upon methanol deuteration argues active proton motions particularly within the first few picoseconds when coherent skeletal motions are underdamped. Pronounced quantum beats are observed for high-frequency modes consisting of strong phenolic COH rocking (1532 cm(-1)) or H-out-of-plane wagging motions (952 cm(-1)) due to anharmonic coupling to coherent low-frequency modes impulsively excited at ca. 96, 120, and 168 cm(-1). The vivid illustration of atomic motions of HPTS in varying H-bonding geometry with neighboring methanol molecules unravels the multidimensional energy relaxation pathways immediately following photoexcitation, and provides compelling evidence that, in lieu of ESPT, the photoacidity of HPTS promptly activates characteristic low-frequency skeletal motions to search phase space mainly concerning the phenolic end and to efficiently dissipate vibrational energy via skeletal deformation and proton shuttling motions within the intermediate, relatively confined excited-state HPTS-methanol complex on a solvent-dependent dynamic potential energy surface.

We report zero kinetic energy photoelectron (ZEKE) spectroscopy of pyrene via resonantly enhanced multiphoton ionization. Our analysis centers on the symmetry of the first electronically excited state (S(1)), its vibrational modes, and the vibration of the ground cationic state (D(0)). From comparisons between the observed vibrational frequencies and those from ab initio calculations at the configuration interaction singles level using the 6-311G (d,p) basis set, and based on other previous experimental and theoretical reports, we confirm the (1)B(2u) symmetry for the S(1) state. This assignment represents a reversal in the energy order of the two closely spaced electronically excited states from our theoretical calculation, and extensive configuration interactions are attributed to this result. Among the observed vibrational levels of the S(1) state, three are results of vibronic coupling due to the nearby second electronically excited state. The ZEKE spectroscopy obtained via the vibronic levels of the S(1) state reveals similar modes for the cation as those of the intermediate state. Although we believe that the ground ionic state can be considered a single electron configuration, the agreement between theoretical and experimental frequencies for the cation is limited. This result is somewhat surprising based on our previous work on cata-condensed polycyclic aromatic hydrocarbons and small substituted aromatic compounds. Although a relatively small molecule, pyrene demonstrates its nonrigidity via several out-of-plane bending modes corresponding to corrugation of the molecular plane. The adiabatic ionization potential of neutral pyrene is determined to be 59 888 ± 7 cm(-1).

Understanding excited-state structural dynamics of fluorescent-protein-based biosensors for Ca(2+) imaging is crucial for developing new in vivo Ca(2+) indicators and advancing bioimaging. We implemented wavelength-tunable femtosecond stimulated Raman spectroscopy (FSRS) with a 530 nm Raman pump to uncover the working mechanism of an intensiometric fluorescent-protein biosensor, G-GECO1.1, highlighting the deprotonation process of its embedded chromophore. Besides confirming the dynamic difference of excited-state proton transfer (ESPT) in the Ca(2+)-free/bound protein, we revealed a chromophore two-ring twisting process with time constants of 36/60 ps that competes with ESPT. In contrast with FSRS data collected using the 800 nm Raman pump, the bluer Raman pump enables us to access a subset of reactant population with partially deprotonated character that exhibits an additional ESPT component on the ∼5 ps time scale. These findings provide deep mechanistic insights into the inhomogeneity and subpopulation-specific conformational dynamics of biosensor chromophores, which will guide the rational design of improved biosensors for metal ion imaging.

Far-IR spectroscopy of pentacene cation, Zhang, et al 2 ABSTRACT The distinctive set of infrared (IR) emission bands at 3. 3, 6.2, 7.7, 8.6, and 11.3 µm are ubiquitously seen in a wide variety of astrophysical environments. They are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, not a single PAH species has yet been identified in space as the mid-IR vibrational bands are mostly representative of functional groups and thus do not allow one to fingerprint individual PAH molecules. In contrast, the far-IR (FIR) bands are sensitive to the skeletal characteristics of a molecule, hence they are important for chemical identification of unknown species. With an aim to offer laboratory astrophysical data for the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and similar future space missions, in this work we report neutral and cation FIR spectroscopy of pentacene (C 22 H 14 ), a five-ring PAH molecule. We report three IR active modes

The ultrafast hydrogen bond breaking and reformation dynamics at the carbonyl site of a coumarin 102 dye molecule in ethanol is captured by femtosecond stimulated Raman spectroscopy (FSRS) on the femtosecond and picosecond timescales.

We report zero kinetic energy (ZEKE) photoelectron spectroscopy of benzo[a]pyrene (BaP) via resonantly enhanced multiphoton ionization (REMPI). Our analysis concentrates on the vibrational modes of the first excited state (S(1)) and those of the ground cationic state (D(0)). Similar to pyrene, another peri-condensed polycyclic aromatic hydrocarbon we have investigated, the first two electronically excited states of BaP exhibit extensive configuration interactions. However, the two electronic states are of the same symmetry, hence vibronic coupling does not introduce any out-of-plane modes in the REMPI spectrum, and Franck-Condon analysis is qualitatively satisfactory. The ZEKE spectra from the in-plane modes observed in the REMPI spectrum demonstrate strong propensity in preserving the vibrational excitation of the intermediate state. Although several additional bands in combination with the vibrational mode of the intermediate state are identifiable, they are much lower in intensity. This observation implies that the molecular structure of BaP has a tremendous capability to accommodate changes in charge density. All observed bands of the cation are IR active, establishing the role of ZEKE spectroscopy in mapping out far infrared bands for astrophysical applications.