Does electronic coherence enhance anticorrelated pigment vibrations under realistic conditions?

The light-harvesting efficiency of a photoactive molecular complex is largely determined by the properties of its electronic quantum states. Those, in turn, are influenced by molecular vibrational states of the nuclear degrees of freedom. Here, we reexamine two recently formulated concepts that a coherent vibronic coupling between molecular states would either extend the electronic coherence lifetime or enhance the amplitude of the anticorrelated vibrational mode at longer times. For this, we study a vibronically coupled dimer and calculate the nonlinear two-dimensional (2D) electronic spectra which directly reveal electronic coherence. The timescale of electronic coherence is initially extracted by measuring the anti-diagonal bandwidth of the central peak in the 2D spectrum at zero waiting time. Based on the residual analysis, we identify small-amplitude long-lived oscillations in the cross-peaks, which, however, are solely due to groundstate vibrational coherence, regardless of having resonant or off-resonant conditions. Our studies neither show an enhancement of the electronic quantum coherence nor an enhancement of the anticorrelated vibrational mode by the vibronic coupling under ambient conditions

Direct laser acceleration of electrons in free-space

Compact laser-driven accelerators are versatile and powerful tools of unarguable relevance on societal grounds for the diverse purposes of science, health, security, and technology because they bring enormous practicality to state-of-the-art achievements of conventional radio-frequency accelerators. Current benchmarking laser-based technologies rely on a medium to assist the light-matter interaction, which impose material limitations or strongly inhomogeneous fields. The advent of few cycle ultra-intense radially polarized lasers has materialized an extensively studied novel accelerator that adopts the simplest form of laser acceleration and is unique in requiring no medium to achieve strong longitudinal energy transfer directly from laser to particle. Here we present the first observation of direct longitudinal laser acceleration of non-relativistic electrons that undergo highly-directional multi-GeV/m accelerating gradients. This demonstration opens a new frontier for direct laser-driven particle acceleration capable of creating well collimated and relativistic attosecond electron bunches and x-ray pulses

Exploring vibrational ladder climbing in vibronic coupling models: Toward experimental observation of a geometric phase signature of a conical intersection

Conical intersections (CIs) have been widely studied using spectroscopic techniques. However, CIs have mainly been identified by rapid internal conversion transitions that take place after the photoexcitation. Such identifications cannot distinguish various types of intersections as well as to separate the actual intersection from an avoided crossing. In this paper, we investigate how ultrafast IR laser pulses can be utilized to stimulate nuclear dynamics revealing geometric phase features associated with CIs. We consider two low-dimensional nonadiabatic models to obtain optimal two- and three-pulse laser sequences for stimulating nuclear dynamics necessary for the CI identification. Our results provide insights on designing non-linear spectroscopic schemes for subsequent probes of the nuclear wavepackets by ultrafast electron diffraction techniques to unambiguously detect CIs in molecules

Synthesis technique and electron beam damage study of nanometer-thin single-crystalline Thymine

Samples suitable for electron diffraction studies must satisfy certain characteristics such as having a thickness in the range of 10 - 100 nm. We report, to our knowledge, the first successful synthesis technique of nanometer-thin sheets of single-crystalline thymine suitable for electron diffraction and spectroscopy studies. This development provides a well defined system to explore issues related to UV photochemistry of DNA and high intrinsic stability essential to maintaining integrity of genetic information. The crystals are grown using the evaporation technique and the nanometer-thin sheets are obtained via microtoming. The sample is characterized via x-ray diffraction (XRD) and is subsequently studied using electron diffraction via a transmission electron microscope (TEM). Thymine is found to be more radiation resistant than similar molecular moieties (e.g., carbamazepine) by a factor of 5. This raises interesting questions about the role of the fast relaxation processes of electron scattering-induced excited states, extending the concept of radiation hardening beyond photoexcited states. The high stability of thymine in particular opens the door for further studies of these ultrafast relaxation processes giving rise to the high stability of DNA to UV radiation

Terahertz-driven linear electron acceleration

The cost, size and availability of electron accelerators is dominated by the achievable accelerating gradient. Conventional high-brightness radio-frequency (RF) accelerating structures operate with 30-50 MeV/m gradients. Electron accelerators driven with optical or infrared sources have demonstrated accelerating gradients orders of magnitude above that achievable with conventional RF structures. However, laser-driven wakefield accelerators require intense femtosecond sources and direct laser-driven accelerators and suffer from low bunch charge, sub-micron tolerances and sub-femtosecond timing requirements due to the short wavelength of operation. Here, we demonstrate the first linear acceleration of electrons with keV energy gain using optically-generated terahertz (THz) pulses. THz-driven accelerating structures enable high-gradient electron or proton accelerators with simple accelerating structures, high repetition rates and significant charge per bunch. Increasing the operational frequency of accelerators into the THz band allows for greatly increased accelerating gradients due to reduced complications with respect to breakdown and pulsed heating. Electric fields in the GV/m range have been achieved in the THz frequency band using all optical methods. With recent advances in the generation of THz pulses via optical rectification of slightly sub-picosecond pulses, in particular improvements in conversion efficiency and multi-cycle pulses, increasing accelerating gradients by two orders of magnitude over conventional linear accelerators (LINACs) has become a possibility. These ultra-compact THz accelerators with extremely short electron bunches hold great potential to have a transformative impact for free electron lasers, future linear particle colliders, ultra-fast electron diffraction, x-ray science, and medical therapy with x-rays and electron beams

Novel applications of Generative Adversarial Networks (GANs) and Convolutional Neural Networks (CNNs) in the analysis of ultrafast electron diffraction (UED) images

We employ generative adversarial networks (GANs) and convolutional neural networks (CNNs) in the study of ultrafast electron diffraction images. We propose a machine learning approach that employs a GAN to convert experimental images into idealized diffraction patterns from which information is extracted via a CNN trained on synthetic data only. We validate this approach on ultrafast electron diffraction (UED) data of bismuth samples undergoing thermalization upon excitation via 800 nm laser pulses. The network was able to predict transient temperatures with a deviation of less than 6% from analytically estimated values. Notably, this performance was achieved on a dataset of 408 images only. We believe employing this network in experimental settings where high volumes of visual data are collected, such as beam lines, could provide insights into the structural dynamics of different samples

Unraveling Quantum Coherences Mediating Primary Charge Transfer Processes in Photosystem II Reaction Center

Photosystem II (PSII) reaction center is a unique protein-chromophore complex that is capable of efficiently separating electronic charges across the membrane after photoexcitation. In the PSII reaction center, the primary energy- and charge-transfer (CT) processes occur on comparable ultrafast timescales, which makes it extremely challenging to understand the fundamental mechanism responsible for the near-unity quantum efficiency of the transfer. Here, we elucidate the role of quantum coherences in the ultrafast energy and CT in the PSII reaction center by performing two-dimensional (2D) electronic spectroscopy at the cryogenic temperature of 20 K, which captures the distinct underlying quantum coherences. Specifically, we uncover the electronic and vibrational coherences along with their lifetimes during the primary ultrafast processes of energy and CT. We also examine the functional role of the observed quantum coherences. To gather further insight, we construct a structure-based excitonic model that provided evidence for coherent energy and CT at low temperature in the 2D electronic spectra. The principles, uncovered by this combination of experimental and theoretical analyses, could provide valuable guidelines for creating artificial photosystems with exploitation of system-bath coupling and control of coherences to optimize the photon conversion efficiency to specific functions

Ultrafast Mid-IR Laser Scalpel: Protein Signals of the Fundamental Limits to Minimally Invasive Surgery

Lasers have in principle the capability to cut at the level of a single cell, the fundamental limit to minimally invasive procedures and restructuring biological tissues. To date, this limit has not been achieved due to collateral damage on the macroscale that arises from thermal and shock wave induced collateral damage of surrounding tissue. Here, we report on a novel concept using a specifically designed Picosecond IR Laser (PIRL) that selectively energizes water molecules in the tissue to drive ablation or cutting process faster than thermal exchange of energy and shock wave propagation, without plasma formation or ionizing radiation effects. The targeted laser process imparts the least amount of energy in the remaining tissue without any of the deleterious photochemical or photothermal effects that accompanies other laser wavelengths and pulse parameters. Full thickness incisional and excisional wounds were generated in CD1 mice using the Picosecond IR Laser, a conventional surgical laser (DELight Er:YAG) or mechanical surgical tools. Transmission and scanning electron microscopy showed that the PIRL laser produced minimal tissue ablation with less damage of surrounding tissues than wounds formed using the other modalities. The width of scars formed by wounds made by the PIRL laser were half that of the scars produced using either a conventional surgical laser or a scalpel. Aniline blue staining showed higher levels of collagen in the early stage of the wounds produced using the PIRL laser, suggesting that these wounds mature faster. There were more viable cells extracted from skin using the PIRL laser, suggesting less cellular damage. β-catenin and TGF-β signalling, which are activated during the proliferative phase of wound healing, and whose level of activation correlates with the size of wounds was lower in wounds generated by the PIRL system. Wounds created with the PIRL systsem also showed a lower rate of cell proliferation. Direct comparison of wound healing responses to a conventional surgical laser, and standard mechanical instruments shows far less damage and near absence of scar formation by using PIRL laser. This new laser source appears to have achieved the long held promise of lasers in minimally invasive surgery