Double resonance spectroscopy reveals structure and dynamics near transition states.

A shared ambition of molecular spectroscopy and molecular dynamics is to establish the truths of chemical intuition on solid physical bedrock. Experimental characterization of the transition state was thought unattainable, but modern techniques have begun to achieve the incredible.

Significantly Improved Detection of Molecular Oxygen by Two-Color Resonance-Enhanced Multiphoton Ionization.

We report a new spectroscopic detection scheme for molecular oxygen that achieves roughly two orders of magnitude higher sensitivity for fully rotationally resolved spectra than the current state of the art. Two-color (2 + 1') resonance-enhanced multiphoton ionization (REMPI) via the 3 Rydberg complex yields state-selective spectra with signal comparable to the intense but diffuse 3σ Π ← Σ (2 + 1) REMPI bands without significant saturation or broadening. The resulting increase in sensitivity permitted observation of the very weak 3π Δ ← Σ transitions and is independent of the intermediate state.

Thermochemical Studies of Small Carbohydrates.

Despite their prevalence in biomass and importance in biochemistry, there is still much to be learned about simple carbohydrates. Gas-phase calculations are reported here on two trioses and three tetroses. For aldotetroses, both the open-chain and furanose forms are considered.

Latency for All: Enabling Latency of Hoveyda-Grubbs Second-Generation Catalysts by Adding Phosphite Ligands.

The Hoveyda-Grubbs catalyst (, M720 Umicore) is among the most widely used catalysts in olefin metathesis reactions. Given the usefulness of and the great interest in developing latent olefin metathesis catalysts for numerous applications, we developed a method to introduce phosphite molecules as ancillary ligands into the precatalyst framework. This modification alters the geometry of the complex from an active -dichloro form to a latent -dichloro species.

Shining Light on Photobleaching: An Artifact That Causes Unnecessary Excitation Among Pathologists.

Context.—: Photobleaching artifact occurs when fluorescence intensity decreases following light exposure. Slides stained with fluorescent techniques may be stored in the dark until primary diagnostics.

Structural and electronic trends of optical cycling centers in polyatomic molecules revealed by microwave spectroscopy of MgCCH, CaCCH, and SrCCH.

The unique optical cycling efficiency of alkaline earth metal-ligand molecules has enabled significant advances in polyatomic laser cooling and trapping. Rotational spectroscopy is an ideal tool for probing the molecular properties that underpin optical cycling, thereby elucidating the design principles for expanding the chemical diversity and scope of these platforms for quantum science. We present a comprehensive study of the structure and electronic properties in alkaline earth metal acetylides with high-resolution microwave spectra of 17 isotopologues of MgCCH, CaCCH, and SrCCH in their ground electronic states.

Direct Observation of the Ethyl Radical in the Pyrolysis of Ethane.

We report the first direct detection of ethyl radical in the pyrolysis of ethane. Observation of this vital intermediate was made possible in this extremely reactive environment by the use of a microreactor coupled with synchrotron radiation and photoelectron photoion coincidence (PEPICO) spectroscopy, despite its short lifetime and low concentration. Together with ab-initio master equation-calculated rates and fully coupled computational fluid dynamics simulations, our measurements show that even under the low pressures and short residence times in our experiment, ethyl formation can only be explained by bimolecular reactions; the most important is the catalytic attack of ethane by H atoms, which are then regenerated by decomposition of the nascent ethyl radicals.

Ionization energies and ionization-induced structural changes in 2-phenylethylamine and its monohydrate.

We report the resonance-enhanced two-photon ionization combined with various detection approaches and quantum chemical calculations of biologically relevant neurotransmitter prototypes, the most stable conformer of 2-phenylethylamine (PEA), and its monohydrate, PEA-HO, to reveal the possible interactions between the phenyl ring and amino group in the neutral and ionic species. Extracting the ionization energies (IEs) and appearance energy was achieved by measuring the photoionization and photodissociation efficiency curves of the PEA parent and photofragment ions, together with velocity and kinetic energy-broadened spatial map images of photoelectrons. We obtained coinciding upper bounds for the IEs for PEA and PEA-HO of 8.

Multispectral and Circular Polarization-Sensitive Carbon Dot-Polydiacetylene Capacitive Photodetector.

Multispectral photodetectors (MSPs) and circularly polarized light (CPL) sensors are important in opto-electronics, photonics, and imaging. A capacitive photodetector consisting of an interdigitated electrode coated with carbon dot/anthraquinone-polydiacetylene is constructed. Photoexcitation of the carbon dots induces transient electron transfer to the anthraquinone moieties, and concomitant change in the film dielectric constant and recorded capacitance.

Franck-Condon spectra of unbound and imaginary-frequency vibrations via correlation functions: A branch-cut free, numerically stable derivation.

Molecular electronic spectra can be represented in the time domain as auto-correlation functions of the initial vibrational wavepacket. We present a derivation of the harmonic vibrational auto-correlation function that is valid for both real and imaginary harmonic frequencies. The derivation rests on Lie algebra techniques that map otherwise complicated exponential operator arithmetic to simpler matrix formulas.

Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation.

We provide compelling experimental and theoretical evidence for the transition state nature of the cyclopropyl cation. Synchrotron photoionization spectroscopy employing coincidence techniques together with a novel simulation based on high-accuracy ab initio calculations reveal that the cation is unstable via its allowed disrotatory ring-opening path. The ring strains of the cation and the radical are similar, but both ring opening paths for the radical are forbidden when the full electronic symmetries are considered.

Kinetic Energy-Broadened Spatial Map Imaging for Recovering Dynamical Information.

The highly successful velocity map imaging (VMI) technique plays a central role in revealing light-matter interactions. Here we demonstrate the related but distinct kinetic energy-broadened spatial map imaging (KESMI) option for recovering KE and angular recoil information on photophysical processes using a VMI system operating in different out-of-focus modes. The characteristic single or double stripes and related steps in the vertical intensity profiles of KESMIs of photoelectrons (PEs) from Ar ionization allow breakthrough developments of a potent global model that enables an understanding and analysis of these patterns.

Maximal kinetic energy and angular distribution analysis of spatial map imaging: Application to photoelectrons from a single quantum state of HO.

Dynamical or spatial properties of charged species can be obtained using electrostatic lenses by velocity map imaging (VMI) or spatial map imaging (SMI), respectively. Here, we report an approach for extracting dynamical and spatial information from patterns in SMI images that map the initial coordinates, velocity vectors, and angular distributions of charged particles onto the detector, using the same apparatus as in VMI. Deciphering these patterns required analysis and modeling, involving both their predictions from convolved spatial and velocity distributions and fitting observed images to kinetic energies (KEs) and anisotropy parameters (βs).

Decomposition of the simplest ketohydroperoxide in the ozonolysis of ethylene.

Hydroperoxides from the ozonolysis of alkenes, in addition to Criegee intermediates, have been proposed as an atmospheric source of OH radicals in the absence of sunlight, but have remained largely elusive due to their reactivity. A weak peroxide bond enables facile OH elimination, and subsequent β-scission can lead to a variety of decomposition products depending on the nature of the peroxide. In this paper we explore this process theoretically for the simplest ketohydroperoxide, hydroperoxyacetaldehyde (HPA), which is believed to be formed in the ozonolysis of ethylene.

The Threshold Photoelectron Spectrum of Fulvenone: A Reactive Ketene Derivative in Lignin Valorization.

Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C H =C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety.

Synchrotron-Based High Resolution Far-Infrared Spectroscopy of -Butadiene.

The high resolution far-infrared spectrum of -butadiene has been reinvestigated by Fourier-transform spectroscopy at two synchrotron radiation facilities, SOLEIL and the Canadian Light Source, at temperatures ranging from 50 to 340 K. Beyond the well-studied bands, two new fundamental bands lying below 1100 cm, ν and ν, have been assigned using a combination of cross-correlation (ASAP software) and Loomis-Wood type (LWWa software) diagrams. While the ν analysis was rather straightforward, ν exhibits obvious signs of a strong perturbation, presumably owing to interaction with the dark ν + ν state.

Photodissociation transition states characterized by chirped pulse millimeter wave spectroscopy.

The 193-nm photolysis of CHCHCN illustrates the capability of chirped-pulse Fourier transform millimeter-wave spectroscopy to characterize transition states. We investigate the HCN, HNC photofragments in highly excited vibrational states using both frequency and intensity information. Measured relative intensities of = 1-0 rotational transition lines yield vibrational-level population distributions (VPD).

High-accuracy extrapolated ab initio thermochemistry. IV. A modified recipe for computational efficiency.

A number of economical modifications to the high-accuracy extrapolated ab initio thermochemistry (HEAT) model chemistry are evaluated. The two resulting schemes, designated as mHEAT and mHEAT+, are designed for efficient and pragmatic evaluation of molecular energies in systems somewhat larger than can be practically studied by the unapproximated HEAT scheme. It is found that mHEAT+ produces heats of formation with nearly subchemical (±1 kJ/mol) accuracy at a substantially reduced cost relative to the full scheme.

Rotational Characterization of the Elusive gauche-Isoprene.

Isoprene (2-methyl-1,3-butadiene) is highly abundant in the atmosphere, second only to methane in hydrocarbon emissions. In contrast to the most stable trans rotamer, structural characterization of gauche-isoprene has proven challenging: it is weakly polar, present at the level of only a few percent at room temperature, and structurally complex due to both torsional and methyl tunneling motions. gauche-Isoprene has been observed by two distinct but complementary experimental approaches: chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy coupled with cryogenic buffer gas cooling, and cavity-enhanced FTMW spectroscopy with a pulsed discharge source.

The Hunt for Elusive Molecules: Insights from Joint Theoretical and Experimental Investigations.

Rotational spectroscopy is an invaluable tool to unambiguously determine the molecular structure of a species, and sometimes even to establish its very existence. This article illustrates how experimental and theoretical state-of-the-art tools can be used in tandem to investigate the rotational structure of molecules, with particular emphasis on those that have long remained elusive. The examples of three emblematic species-gauche-butadiene, disilicon carbide, and germanium dicarbide-highlight the close, mutually beneficial interaction between high-level theoretical calculations and sensitive microwave measurements.

Thermal Decompositions of the Lignin Model Compounds: Salicylaldehyde and Catechol.

The nascent steps in the pyrolysis of the lignin components salicylaldehyde ( o-HOCHCHO) and catechol ( o-HOCHOH) were studied in a set of heated microreactors. The microreactors are small (roughly 1 mm ID × 3 cm long); transit times through the reactors are about 100 μs. Temperatures in the microreactors can be as high as 1600 K, and pressures are typically a few hundred torr.

Butadiene and Heterodienes Revisited.

Surprising features in a recently published high-level calculation of the rotational profile of butadiene led us to compare butadiene with a set of 17 heterodienes. The rotational profiles for this large group of compounds varied widely, thereby possessing a high information content. These data were subjected to a Fourier analysis yielding 1- through 6-fold terms: the one-fold terms represent the change in steric energy on going from 180° to 0°, while the changes in the 2-fold terms correspond to the expected change in π-delocalization energy with structure; the 3-fold terms were significant and found to be linearly correlated to the average of the atomic charges of the atoms at the central single bond of the cis-forms, but their origins are still not clear; we propose a novel 1,4 π-interactions that may account for this phenomenon.

The Molecular Structure of gauche-1,3-Butadiene: Experimental Establishment of Non-planarity.

The planarity of the second stable conformer of 1,3-butadiene, the archetypal diene for the Diels-Alder reaction in which a planar conjugated diene and a dienophile combine to form a ring, is not established. The most recent high level calculations predicted the species to adopt a twisted, gauche structure owing to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the double bonds. The structure cis-1,3-butadiene is unambiguously confirmed experimentally to indeed be gauche with a substantial dihedral angle of 34°, in excellent agreement with theory.

Active Thermochemical Tables: The Adiabatic Ionization Energy of Hydrogen Peroxide.

The adiabatic ionization energy of hydrogen peroxide (HOOH) is investigated, both by means of theoretical calculations and theoretically assisted reanalysis of previous experimental data. Values obtained by three different approaches: 10.638 ± 0.

Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products.

We report the combination of tabletop vacuum ultraviolet photoionization with photoion-photoelectron coincidence spectroscopy for sensitive, isomer-specific detection of nascent products from a pyrolysis microreactor. Results on several molecules demonstrate two essential capabilities that are very straightforward to implement: the ability to differentiate isomers and the ability to distinguish thermal products from dissociative ionization. Here, vacuum ultraviolet light is derived from a commercial tabletop femtosecond laser system, allowing data to be collected at 10 kHz; this high repetition rate is critical for coincidence techniques.