arXiv subjects

Guido W. Fuchs

Publications and source records attributed to Guido W. Fuchs.

12 recordsLinked to original sources

arXiv2025

Heavier chalcogenofenchones for fundamental gas-phase studies of molecular chirality

Monoterpene ketones are frequently studied compounds that enjoy great popularity both in chemistry and in physics due to comparatively high volatility, stability, conformational rigidity and commercial availability. Herein, we explore the heavier chalcogenoketone derivatives of fenchone as promising benchmark systems -- synthetically accessible in enantiomerically pure form -- for systematic studies of nuclear charge ($Z$) dependent properties in chiral compounds. Synthesis, structural characterization, thorough gas-phase rotational and vibrational spectroscopy as well as accompanying quantum chemical studies on the density-functional-theory level reported in this work foreshadow subsequent applications of this compound class for fundamental investigations of molecular chirality under well-defined conditions.

physics.chem-ph↗

arXiv2025

Excited state assignment and state-resolved photoelectron circular dichroism in chalcogen-substituted fenchones

Excited electronic states of fenchone, thiofenchone, and selenofenchone are characterized and assigned with different gas-phase spectroscopic methods and \textit{ab initio} quantum chemical calculations. With an increasing atomic number of the chalcogen, we observe increasing bathochromic (red) shifts, which vary in strength for Rydberg states, valence-excited states, and ionization energies. The spectroscopic insight is used to state-resolve the contributions in multi-photon photoelectron circular dichroism with femtosecond laser pulses. This is shown to be a sensitive observable of molecular chirality in all studied chalcogenofenchones. Our work contributes new spectroscopic information, particularly on thiofenchone and selenofenchone. It may open a perspective for future coherent control experiments exploiting resonances in the visible and or near-ultraviolet spectral regions.

physics.chem-ph↗

arXiv2024

Strong coupling of a chiral molecule with circularly polarised modes inside a cavity

We consider the discriminatory interaction of a chiral molecule with circularly polarised modes inside a cavity. Starting from a generalised Jaynes--Cummings model that includes both electric and magnetic dipole couplings, we derive the Rabi frequency and associated Casimir--Polder potential for a cavity with a single mode of given handedness. One finds that both acquire a discriminatory component whose sign depends on the relative handedness of molecule and cavity mode. We generalise this result to a cavity that supports two modes of different handedness on the basis of superradiant collective field states.

quant-ph↗

arXiv2021

The Rotationally Resolved Infrared Spectrum of TiO and Its Isotopologues

In this study, we present the ro-vibrationally resolved gas-phase spectrum of the diatomic molecule TiO around 1000\,cm$^{-1}$. Molecules were produced in a laser ablation source by vaporizing a pure titanium sample in the atmosphere of gaseous nitrous oxide. Adiabatically expanded gas, containing TiO, formed a supersonic jet and was probed perpendicularly to its propagation by infrared radiation from quantum cascade lasers. Fundamental bands of $^{46-50}$TiO and vibrational hotbands of $^{48}$TiO are identified and analyzed. In a mass-independent fitting procedure combining the new infrared data with pure rotational and electronic transitions from the literature, a Dunham-like parameterization is obtained. From the present data set, the multi-isotopic analysis allows to determine the spin-rotation coupling constant $γ$ and the Born-Oppenheimer correction coefficient $Δ_{\rm U_{10}}^{\mathrm{Ti}}$ for the first time. The parameter set enables to calculate the Born-Oppenheimer correction coefficients $Δ_{\rm U_{02}}^{\mathrm{Ti}}$ and $Δ_{\rm U_{02}}^{\mathrm{O}}$. In addition, the vibrational transition moments for the observed vibrational transitions are reported.

physics.atom-ph↗

arXiv2021

Deciphering the Rotational Spectrum of the First Excited Torsional State of Propylene Oxide

The first excited torsional state of the chiral molecule propylene oxide, $\mathrm{CH_{3}C_{2}H_{3}O}$, is investigated from millimeter up to sub-millimeter wavelengths (75-950 GHz). The first excited vibrational mode of propylene oxide, $\upsilon_{24}$, is analysed using the programs ERHAM and XIAM. Rotational constants and tunneling parameters are provided, and a description of the A-E splittings due to internal rotation is given. Furthermore, the potential barrier height to internal rotation $V_{3}$ is determined to be $V_{3} = 894.5079(259) \mathrm{cm^{-1}}$ . Our results are compared with quantum chemical calculations and literature values. We present a line list of the dense spectrum of the first excited torsional state of propylene oxide in the (sub-)millimeter range. Our results will be useful for further studies of chiral molecules in vibrationally excited states, and will enable astronomers to search for rotational transitions originating from $\upsilon_{24}$ of propylene oxide in interstellar space.

physics.chem-ph↗

arXiv2021

Laboratory blueprints for interstellar searches of aromatic chiral molecules: rotational signatures of styrene oxide

The tracking of symmetry-breaking events in space is a longlasting goal of astrochemists, aiming at an understanding of homochiral Earth chemistry. One current effort at this frontier aims at the detection of small chiral molecules in the interstellar medium. For that, high-resolution laboratory spectroscopy data is required, providing blueprints for the search and assignment of these molecules using radioastronomy. Here, we used chirped-pulse Fourier transform microwave and millimeter-wave spectroscopy and frequency modulation absorption spectroscopy to record and assign the rotational spectrum of the chiral aromatic molecule styrene oxide, $\mathrm{C_{6}H_{5}C_{2}H_{3}O}$, a relevant candidate for future radioastronomy searches. Using experimental data from the 2-12, 75-110, 170-220, and 260-330 GHz regions, we performed a global spectral analysis, complemented by quantum chemistry calculations. A global fit of the ground state rotational spectrum was obtained, including rotational transitions from all four frequency regions. Primary rotational constants as well as quartic and sextic centrifugal distortion constants were determined. We also investigated vibrationally excited states of styrene oxide, and for the three lowest vibrational states, we determined rotational constants including centrifugal distortion corrections up to the sextic order. In addition, spectroscopic parameters for the singly-substituted $^{13}$C and $^{18}$O isotopologues were retrieved from the spectrum in natural abundance and used to determine the effective ground state structure of styrene oxide in the gas phase. The spectroscopic parameters and line lists of rotational transitions obtained here will assist future astrochemical studies of this class of chiral organic molecules.

astro-ph.IM↗

arXiv2021

Mass-independent analysis of the stable isotopologues of gas-phase titanium monoxide -- TiO

More than 130 pure rotational transitions of $^{46}$TiO, $^{47}$TiO, $^{48}$TiO, $^{49}$TiO, $^{50}$TiO, and $^{48}$Ti$^{18}$O are recorded using a high-resolution mm-wave supersonic jet spectrometer in combination with a laser ablation source. For the first time a mass-independent Dunham-like analysis is performed encompassing rare titanium monoxide isotopologues, and are compared to results from high-accuracy quantum-chemical calculations. The obtained parametrization reveals for titanium monoxide effects due to deviations from the Born-Oppenheimer approximation. Additionally, the dominant titanium properties enable an insight into the electronic structure of TiO by analyzing its hyperfine interactions. Further, based on the mass-independent analysis, the frequency positions of the pure rotational transitions of the short lived rare isotopologue $^{44}$TiO are predicted with high accuracy, i.e., on a sub-MHz uncertainty level. This allows for dedicated radio-astronomical searches of this species in core-collapse environments of supernovae.

physics.chem-ph↗

arXiv2021

The Millimeter-Wave Spectrum of Doubly Deuterated Propylene Oxide CH$_3$CHCD$_2$O

Spectra of doubly deuterated propylene oxide, CH$_3$CHCD$_2$O, were recorded in the millimeter-wave spectral region up to 330 GHz utilizing a 2f frequency modulated Terahertz spectrometer. Rotational and centrifugal distortion constants and tunneling parameters for the description of the internal rotation of the methyl group were retrieved. The software XIAM was used to describe the A-E tunneling splitting with a frequency uncertainty of 82 kHz. Molecular parameters derived from our measurements are complemented by quantum chemical anharmonic frequency calculations on the B3LYP/augcc-pVTZ level of theory. In addition, the barrier height to internal rotation of the methyl group,V3, was derived experimentally and found to slightly differ from the value reported for the main isotopologue. In view of astrophysical observations we provide accurate line lists to search for doubly deuterated propylene oxide in space. Furthermore, we deliver improved molecular parameters to further investigate the properties of a simple chiral molecule possessing internal large amplitude motions.

physics.chem-ph↗

arXiv2019

First detection of the carbon chain molecules 13CCC and C13CC towards SgrB2(M)

We report the first detection of the isotopologues 13CCC and C13CC. We used the heterodyne receivers GREAT and upGREAT on board SOFIA to search for the ro-vibrational transitions Q(2) and Q(4) of 13CCC and C13CC at 1.9 THz along the line of sight towards SgrB2(M). For both species the ro-vibrational absorption lines Q(2) and Q(4) have been identified, primarily arising from the warm gas physically associated with the strong continuum source SgrB2(M). In addition, to determine the local excitation temperature we analyzed data from nine ro-vibrational transitions of the main isotopologue CCC in the frequency range between 1.6-1.9 THz which were taken from the Herschel Science Data Archive, and derived a gas excitation temperature of Tex = 44.4(+4.7/-3.9) K and a total column density of N(CCC)=3.88(+0.39/-0.35)x10^15 cm^-2. Assuming the excitation temperatures of C13CC and 13CCC to be the same as for CCC, we obtained column densities of the 13C-isotopologues of N(C13CC) = 2.1(+0.9/-0.6)X10^14 cm^-2 and N(13CCC)=2.4(+1.2/-0.8)x10^14 cm^-2. The derived 12C/13C abundance ratio in the C3 molecules is 20.5(4.2), which is in agreement with the elemental ratio of 20, typically observed in SgrB2(M). However, we find the N(13CCC) / N(C13CC) ratio to be 1.2(0.1), which is shifted from the statistically expected value of 2. We propose that the discrepant abundance ratio arises due to the lower zero-point energy of C13CC which makes position exchange reaction converting 13CCC to C13CC energetically favorable.

astro-ph.GA↗

arXiv2007

Band profiles and band strengths in mixed H2O:CO ices

A laboratory study on the band profiles and band strengths of H2O in CO ice, and vice versa, is presented and interpreted in terms of two models. The results show that a mutual interaction takes place between the two species in the solid, which alters the band positions and band strengths. It is found that the band strengths of the H2O bulk stretch, bending and libration vibrational bands decrease linearly by a factor of up to 2 when the CO concentration is increased from 0 to 80%. By contrast, the band strength of the free OH stretch increases linearly. The results are compared to a recently performed quantitative study on H2O:CO2 ice mixtures. It is shown that for mixing ratios of 1:0.5 H2O:X and higher, the H2O bending mode offers a good tracer to distinguish between CO2 or CO in H2O ice. Additionally, it is found that the band strength of the CO fundamental remains constant when the water concentration is increased in the ice. The integrated absorbance of the 2152 cm-1 CO feature, with respect to the total integrated CO absorption feature, is found to be a good indicator of the degree of mixing of CO in the H2O:CO laboratory ice system. From the change in the H2O absorption band strength in laboratory ices upon mixing we conclude that astronomical water ice column densities on various lines of sight can be underestimated by up to 25% if significant amounts of CO and CO2 are mixed in.

astro-ph↗

arXiv2007

Photodesorption of CO ice

At the high densities and low temperatures found in star forming regions, all molecules other than H2 should stick on dust grains on timescales shorter than the cloud lifetimes. Yet these clouds are detected in the millimeter lines of gaseous CO. At these temperatures, thermal desorption is negligible and hence a non-thermal desorption mechanism is necessary to maintain molecules in the gas phase. Here, the first laboratory study of the photodesorption of pure CO ice under ultra high vacuum is presented, which gives a desorption rate of 3E-3 CO molecules per UV (7-10.5 eV) photon at 15 K. This rate is factors of 1E2-1E5 larger than previously estimated and is comparable to estimates of other non-thermal desorption rates. The experiments constrains the mechanism to a single photon desorption process of ice surface molecules. The measured efficiency of this process shows that the role of CO photodesorption in preventing total removal of molecules in the gas has been underestimated.

astro-ph↗

arXiv2006

Effects of CO2 on H2O band profiles and band strengths in mixed H2O:CO2 ices

H2O is the most abundant component of astrophysical ices. In most lines of sight it is not possible to fit both the H2O 3 um stretching, the 6 um bending and the 13 um libration band intensities with a single pure H2O spectrum. Recent Spitzer observations have revealed CO2 ice in high abundances and it has been suggested that CO2 mixed into H2O ice can affect relative strengths of the 3 um and 6 um bands. We used laboratory infrared transmission spectroscopy of H2O:CO2 ice mixtures to investigate the effects of CO2 on H2O ice spectral features at 15-135 K. We find that the H2O peak profiles and band strengths are significantly different in H2O:CO2 ice mixtures compared to pure H2O ice. In all H2O:CO2 mixtures, a strong free-OH stretching band appears around 2.73 um, which can be used to put an upper limit on the CO2 concentration in the H2O ice. The H2O bending mode profile also changes drastically with CO2 concentration; the broad pure H2O band gives way to two narrow bands as the CO2 concentration is increased. This makes it crucial to constrain the environment of H2O ice to enable correct assignments of other species contributing to the interstellar 6 um absorption band. The amount of CO2 present in the H2O ice of B5:IRS1 is estimated by simultaneously comparing the H2O stretching and bending regions and the CO2 bending mode to laboratory spectra of H2O, CO2, H2O:CO2 and HCOOH.

astro-ph↗