A systematic model study quantifying how conical intersection topography modulates photochemical reactions.

Despite their important role in photochemistry and expected presence in most polyatomic molecules, conical intersections have been thoroughly characterized in a comparatively small number of systems. Conical intersections can confer molecular photoreactivity or photostability, often with remarkable efficacy, due to their unique structure: at a conical intersection, the adiabatic potential energy surfaces of two or more electronic states are degenerate, enabling ultrafast decay from an excited state without radiative emission, known as nonadiabatic transfer. Furthermore, the precise conical intersection topography determines fundamental properties of photochemical processes, including excited-state decay rate, efficacy, and molecular products that are formed. However, these relationships have yet to be defined comprehensively. In this article, we use an adaptable computational model to investigate a variety of conical intersection topographies, simulate resulting nonadiabatic dynamics, and calculate key photochemical observables. We varied the vibrational mode frequencies to modify conical intersection topography systematically in four primary classes of conical intersections and quantified the resulting rate, total yield, and product yield of nonadiabatic decay. The results reveal that higher vibrational mode frequencies reduce nonadiabatic transfer, but increase the transfer rate and resulting photoproduct formation. These trends can inform progress toward experimental control of photochemical reactions or tuning of molecules' photochemical properties based on conical intersections and their topography.

Nonadiabatic Photochemistry Induced by Inaccessible Conical Intersections.

Conical intersections are ubiquitous in photochemical processes, where nonadiabatic transfer induces ultrafast nonradiative decay from an excited state. Although they eluded experimental detection until the 1990s, today three diagnostic attributes are generally associated with photochemical reactions through conical intersections: ultrafast electronic dynamics, negligible fluorescence, and coherent wavepacket transfer. Here, we use generalized quantum dynamics simulations to show that coherent nonadiabatic transfer of excited vibrational wavepackets can occur even without reaching the conical intersection region. Instead, the wavepacket remains distant from the conical intersection throughout. In some topographies, an energetically inaccessible conical intersection can be completely avoided, yet still induce substantial nonadiabatic transfer with ultrafast transfer efficiencies that are nearly identical to those of direct transfer through a conical intersection. These results reveal that the diagnostic properties of conical intersections are not actually specific to decay pathways traveling directly through the intersection funnel, as is the common interpretation, but can also arise from alternative pathways that do not reach the intersection. This suggests that the diagnostic features and experimental signals associated with conical intersections should be reassessed, and the concept of pathways through a conical intersection as the "paradigm of photochemistry" may need to be adjusted.

Femtosecond pulse compression using a neural-network algorithm.

A key requirement for femtosecond spectroscopy measurements is to compress the laser pulse to its transform-limited duration. In particular, for few-cycle laser pulses, the compression process is time-consuming using conventional algorithms that converge statistically. Here we show that machine learning can accelerate the process of pulse compression: we have developed an adaptive neural-network algorithm to control a deformable-mirror-based pulse shaper that converges 100× faster than a standard evolutionary algorithm.

Chiroptical structure-property relations in cyclo[18]carbon and its in silico hydrogenation products.

The anisotropy of the optical activity of cyclo[18]carbon (C18 ), fully hydrogenated C18 (C18 H36 ), and 26 hydrogenated compounds of intermediate composition, C18 H2n , n = 1,2…17, were computed. These compounds were selected because they resemble loops of wire. The maximum gyration for acetylenic and cumulenic subgroups of compounds was linearly proportional to the product of the geometric area over which the charge can circulate, multiplied by the largest separation between carbon atoms on opposing sides of the loops. These geometric quantities can be likened to transition magnetic dipole moments and transition electric dipole moments, respectively, that can be generated in electronic excitations and which contribute in the main to nonresonant optical activity. The correlation between a computed geometric product of distance and area, and a quantum chemical property, establishes that chiroptical structure-activity relationships can be well established for judiciously chosen series of comparatively large compounds.

Simultaneous neuron- and astrocyte-specific fluorescent marking.

Systematic and simultaneous analysis of multiple cell types in the brain is becoming important, but such tools have not yet been adequately developed. Here, we aimed to generate a method for the specific fluorescent labeling of neurons and astrocytes, two major cell types in the brain, and we have developed lentiviral vectors to express the red fluorescent protein tdTomato in neurons and the enhanced green fluorescent protein (EGFP) in astrocytes. Importantly, both fluorescent proteins are fused to histone 2B protein (H2B) to confer nuclear localization to distinguish between single cells. We also constructed several expression constructs, including a tandem alignment of the neuron- and astrocyte-expression cassettes for simultaneous labeling. Introducing these vectors and constructs in vitro and in vivo resulted in cell type-specific and nuclear-localized fluorescence signals enabling easy detection and distinguishability of neurons and astrocytes. This tool is expected to be utilized for the simultaneous analysis of changes in neurons and astrocytes in healthy and diseased brains.

E to Z Photoisomerization of Phytochrome Cph1Δ Exceeds the Born-Oppenheimer Adiabatic Limit.

The Born-Oppenheimer adiabatic limit applies broadly in chemistry because most reactions occur on the ground electronic state. Photochemical reactions involve two or more electronic states and need not be subject to this adiabatic limit. The spectroscopic signatures of nonadiabatic processes are subtle, and therefore, experimental investigations have been limited to the few systems dominated by single photochemical outcomes. Systems with branched excited-state pathways have been neglected, despite their potential to reveal insights into photochemical reactivity. Here we present experimental evidence from coherent three-dimensional electronic spectroscopy that the E to Z photoisomerization of phytochrome Cph1 is strongly nonadiabatic, and the simulations reproduce the measured features only when the photoisomerization proceeds nonadiabatically near, but not through, a conical intersection. The results broaden the general understanding of photoisomerization mechanisms and motivate future studies of nonadiabatic processes with multiple outcomes arising from branching on excited-state potential energy surfaces.