Wavelength dependent photoelectron circular dichroism of limonene studied by femtosecond multiphoton laser ionization and electron-ion coincidence imaging

Enantiomers of the monoterpene limonene have been investigated by (2+1) resonance enhanced multiphoton ionization and photoelectron circular dichroism employing tuneable, circularly polarized femtosecond laser pulses. Electron imaging detection provides 3D momentum measurement while electron-ion coincidence detection can be used to mass-tag individual electrons. Additional filtering, by accepting only parent ion tagged electrons, can be then used to provide discrimination against higher energy dissociative ionization mechanisms where more than three photons are absorbed to better delineate the two photon resonant, one photon ionization pathway. The promotion of different vibrational levels and, tentatively, different electronic ion core configurations in the intermediate Rydberg states can be achieved with different laser excitation wavelengths (420 nm, 412 nm, and 392 nm), in turn producing different state distributions in the resulting cations. Strong chiral asymmetries in the lab frame photoelectron angular distributions are quantified, and a comparison made with a single photon (synchrotron radiation) measurement at an equivalent photon energy

The Rydberg 3p multiplet structure of the fenchone C band absorption

The vibrationally structured 3p Rydberg excitation is identified and assigned in the VUV absorption spectrum of fenchone with an origin at 6.31 eV, below the prominent 6.4 eV C̃ (nominally 3p) band onset. This feature cannot, however, be observed in (2+1) REMPI spectra, as its relative excitation cross-section is much reduced in a two-photon transition. The 3p and 3p excitation thresholds, found to differ by only 10-30 meV, lie around 6.4 eV corresponding to the first intense C̃ band peak in both VUV and REMPI spectra. Calculations of vertical and adiabatic Rydberg excitation energies, photon absorption cross-sections, and vibrational profiles are used to support these interpretations

An imaging photoelectron-photoion coincidence investigation of homochiral 2R,3R-butanediol clusters

We report an experimental investigation of homochiral cluster formation in seeded molecular beam expansions of (2R,3R)-butanediol. Synchrotron radiation VUV photoionization measurements have been performed using a double imaging electron-ion spectrometer in various configurations and modes of operation. These include measurements of the cluster ion mass spectra and wavelength scanned ion yields and threshold electron spectra. Protonated cluster ions ranging up to n=7 have been observed and size-selected photoelectron spectra and photoelectron circular dichroism (PECD) have been recorded by velocity map imaging at a number of fixed photon energies. Translation temperatures of the cluster ions have been further examined by ion imaging measurements. As well as the sequence of protonated clusters with integral numbers of butanediol monomer units, a second series with half-integral monomer masses is observed and deduced to result from a facile cleavage of a butanediol monomer moiety within the nascent cluster. This second sequence of half-integral masses displays quite distinct behaviours. PECD measurements are used to show that the half-integral mass clusters ions do not share a common parentage with whole integer masses. Using an analogy developed with simple theoretical calculations of butanediol dimer structures, it is inferred that the dissociative branching into integral and half-integral ion mass sequences is controlled by the presence of different butanediol monomer conformations within the hydrogen bonded clusters

Decoupling vibration and electron energy dependencies in the photoelectron circular dichroism of a terpene, 3-carene

A fresh perspective on the interaction of electron and nuclear motions in photon induced dynamical processes can be provided by the coupling of photoelectron angular distributions and cation vibrational states in the photoionization of chiral molecules using circularly polarized radiation. The chiral contributions, manifesting as a forward-backward asymmetry in the photoemission, can be assessed using Photoelectron Circular Dichroism (PECD), which has revealed an enhanced vibrational influence exerted on the outgoing photoelectron. In this paper, we investigate the PECD of a rigid chiral monoterpene, 3-carene, using single-photon vacuum ultraviolet ionization by polarized synchrotron radiation and selecting energies from the ionization threshold up to 19.0 eV. By judicious choice of these photon energies, two factors that influence PECD asymmetry values, electron kinetic energy and ion vibrational level, can be effectively isolated, allowing a clear demonstration of the very marked vibrational effects. A slow photoelectron spectrum is used to examine the vibrational structure of the isolated outermost valence (HOMO) photoelectron band, and peak assignments are made with the aid of a Franck-Condon simulation. Together, these provide an estimate of the adiabatic ionization energy as 8.385 eV. The reported chiral asymmetry from the randomly oriented 3-carene enantiomers reaches a maximum of over 21%. Theoretical PECD calculations, made both for the fixed equilibrium molecular geometry and also modeling selected normal mode vibration effects, are presented to provide further insight

Vibration dependent branching and photoelectron angular distributions observed across the Cooper minimum region of bromobenzene

Vibrational state-resolved photoelectron anisotropy parameters, beta, for the ~X 2B1, ~B 2B2, and ~C2B1 state ionizations of bromobenzene have been recorded at photon energies ranging from 20.5 to 94 eV, so spanning the region of the expected bromine Cooper minimum (CM). The ~X state displays no CM and its beta value is also independent of vibrational level, in accord with the Franck-Condon Approximation. The ~B and ~ C state beta values display the CM to differing degrees, but both show a vibrational dependence that extends well below the obvious CM dip. Calculations are presented that replicate these observations of Franck-Condon Approximation breakdown spanning an extended photon energy range. This is the first demonstration of such wide-ranging breakdown detected in the beta anisotropy parameter in the absence of any resonance. Measured and calculated vibrational branching ratios for these states are also presented. Although the ~B state branching ratios remain constant, in accord with Franck-Condon expectations, the ~X and (especially) the ~C state ratios display weak, quasi-linear variations across the studied range of photon energy, but with no apparent correlation with the CM position

An Experimental and Theoretical Investigation of the 3sp(d) Rydberg States of Fenchone by Polarized laser Resonance-Enhanced-Multiphoton-ionization and Fourier Transform VUV Absorption Spectroscopy

The VUV absorption spectrum of fenchone is re‐examined using Fourier transform spectrometry, revealing new vibrational structure. Picosecond laser (2+1) resonance enhanced multiphoton ionization (REMPI) spectroscopy complements this, providing an alternative view of 3 spd Rydberg excitations. These spectra are broadly similar, with minor differences that are largely explained by referring to calculated one‐ and two‐photon electronic excitation cross‐sections. Both show good agreement with Franck‐Condon simulations of the vibrational structure. Parent ion REMPI yields are studied as a function of laser polarization and intensity, the latter providing insight into the relative two‐photon excitation and one‐photon ionization rates. The experimental circular‐linear dichroism observed in the parent ion yields varies strongly between the 3 s and 3 p Rydberg states, in good overall agreement with the calculated two‐photon excitation circular‐linear dichroism, while corroborating other evidence that the 3p z sub‐state plays no more than a very minor role in the (2+1) REMPI spectrum. Vibrationally resolved photoelectron spectra are recorded with picosecond pulse duration (2+1) REMPI at selected intermediate vibrational excitations. The 3 s intermediate state displays a very strong Δ v =0 propensity on ionization, but the 3 p intermediate evidences more complex vibronic dynamics, and we infer some 3 p‐ 3 s internal conversion prior to ionization

Vibrationally-resolved photoelectron spectroscopy and photoelectron circular dichroism of bicyclic monoterpene enantiomers

The photoionization of four chiral bicyclic monoterpene isomers, α-pinene, β-pinene, 3-carene and sabinene — all commonly found constituents in essential natural oils — has been studied using synchrotron radiation and compared to recent findings for the cyclic isomer limonene. Slow photoelectron spectra (SPES) are recorded between threshold and an energy of 10.5 eV. In the case of limonene, α-pinene, and 3-carene, vibrational structure is observed in the ground ionic state and attributed to a CC double bond stretching in the cation, using Franck-Condon vibrational band simulations. The photoelectron circular dichroism (PECD) is examined for specific enantiomers of these terpenes, and vibrational modification of the forward-backward photoelectron asymmetry detected by PECD can be tentatively identified, even when the corresponding SPES is unstructured. Large chiral asymmetry factors are found at low binding energies for the pinenes and 3-carene, with α-pinene in particular displaying a 37% forward-backward photoelectron asymmetry, believed to be a record chiroptical asymmetry for randomly-oriented, non-interacting molecules

An experimental and theoretical study of the valence shell photoelectron spectrum of oxalyl chloride

Polarization dependent photoelectron spectra encompassing the outer valence orbitals of oxalyl chloride have been recorded in the photon energy range 19 – 91 eV. These have allowed photoelectron anisotropy parameters and branching ratios to be determined. Photoionization partial cross sections and photoelectron anisotropy parameters have been calculated with the Continuum Multiple Scattering – Xα approach. Four of the outer valence orbitals are predicted to possess a significant Cl 3p lone-pair character and have closely grouped binding energies. The photoionization dynamics of these four orbitals are predicted to be strongly affected by the Cooper minimum associated with the Cl 3p orbital in the isolated atom at photon energies around 40 eV. A comparison between the theoretical and measured photoelectron anisotropy parameters has enabled the molecular orbital sequence to be clarified. A doublet has been observed in the region of the photoelectron spectrum where a band due to the 5bu orbital might be anticipated. Our calculations indicate that the 6bu and 5bu orbitals are coupled. This coupling may account for the apparent lack of a pronounced Cooper minimum in the β-parameter associated with the nominal 6bu ionization and for the unexpected appearance of the adjacent photoelectron band, nominally associated with the 5bu orbital. The vertical ionization energy of the outermost 7ag orbital was experimentally determined to be 11.266±0.005 eV