Excited state intramolecular proton transfer (ESIPT) of 1-hydroxy-2-acetonaphthone (HAN) has been in controversy, mainly because its Stokes shift is small compared to those of typical ESIPT molecules. We have investigated excited state dynamics of HAN by time-resolved fluorescence with a resolution high enough to record the nuclear wave packet motions in the excited state. Population dynamics of both the normal and tautomer forms were recorded together with the wave packet motions of the tautomer in the excited state, which confirm the ESIPT of HAN. The population dynamics of the normal and tautomer forms imply that the ESIPT dynamics is biphasic with two time constants <25 and 80 fs. Theoretical analysis of the vibrational modes of the tautomer excited impulsively reveals that major part of the change for the ESIPT reaction is on the naphthalene ring.

Detailed molecular dynamics simulations of an acid-base reaction have been the subject of extensive investigations. Here we report the excited state proton transfer dynamics of pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in acetate buffer by time-resolved fluorescence (TF) and quantum mechanical/effective fragment potential molecular dynamics (QM/EFP-MD) simulations. High time resolution in TF and TF spectra measurements allows the acquisition of accurate reaction kinetics. Upon the photoexcitation of HPTS, the proton (deuterium) is transferred coherently to acetate in 60 fs (80 fs) for a contact pair of HPTS (DPTS) and acetate by a hydrogen bond, which comprises approximately 28% of the population. ESPT proceeds slowly on a picosecond time scale for the remaining HPTS as reported previously. Coherent wave packet motions of the reactant (acid) and the product (conjugate base) enable the acquisition of the vibrational spectra of excited states via TF (VETF). A comparison of the VETFs of the reactant and the product and the calculation of the Huang-Rhys factors (vibrational reorganization energies) identify the vibrational modes that actively participate in the coherent proton transfer. In particular, the 246 cm vibrational mode, which consists of in-plane skeletal stretching motion, promotes the ESPT by transferring the donor oxygen towards the acceptor oxygen in acetate. QM/EFP MD simulations corroborate the experiment and provide molecular details of the ESPT.

The effects of epitaxial materials and solar cell design on the performance of solar cells grown by the multilayer approach are investigated. The novel solar cell structure with a p‐on‐n type configuration suggested exhibits improved uniformity in the photovoltaic performance because of the suppression of Zn diffusion. This approach provides routes to achieve further improvements and acts as a guideline for the commercialization of the multilayer technique.

SUMMARY Hidden Markov models (HMMs) are used to learn single-molecule kinetics across a range of experimental techniques. By their construction, HMMs assume that single-molecule events occur on slower timescales than those of data acquisition. To move beyond that HMM limitation and allow for single-molecule events to occur on any timescale, we must treat single-molecule events in continuous time as they occur in nature. We propose a method to learn kinetic rates from single-molecule Förster resonance energy transfer (smFRET) data collected by integrative detectors, even if those rates exceed data acquisition rates. To achieve that, we exploit our recently proposed “hidden Markov jump process” (HMJP), with which we learn transition kinetics from parallel measurements in donor and acceptor channels. HMJPs generalize the HMM paradigm in two critical ways: (1) they deal with physical smFRET systems as they switch between conformational states in continuous time , and (2) they estimate transition rates between conformational states directly without having recourse to transition probabilities or assuming slow dynamics. Our continuous-time treatment learns the transition kinetics and photon emission rates for dynamic regimes that are inaccessible to HMMs, which treat system kinetics in discrete time. We validate our framework’s robustness on simulated data and demonstrate its performance on experimental data from FRET-labeled Holliday junctions.

Single-molecule Förster resonance energy transfer (smFRET) is widely utilized to investigate the structural heterogeneity and dynamics of biomolecules. However, it has been difficult to simultaneously achieve a wide observation time window, a high structure resolution, and a high time resolution with the current smFRET methods. Herein, we introduce a new method utilizing two-dimensional fluorescence lifetime correlation spectroscopy (2D FLCS) and surface immobilization techniques. This method, scanning 2D FLCS, enables us to examine the structural heterogeneity and dynamics of immobilized biomolecules on a time scale from microsecond to subsecond by slowly scanning the sample stage at the rate of ∼1 μm/s. Application to the DNA Holliday junction (HJ) complex under various [Mg2+] conditions demonstrates that scanning 2D FLCS enables tracking reaction kinetics from 25 μs to 30 ms with a time resolution as high as 1 μs. Furthermore, the high structure resolution of scanning 2D FLCS allows us to unveil the ensemble nature of each isomer state and the heterogeneity of the dynamics of the HJ.