Rotational spectra induced by vibrations

Mizushima and Venkateswarlu showed in 1953 that certain molecules have the property that excited vibrational states may possess rotational spectra even when the rotational spectrum of the ground vibrational state is forbidden by symmetry. We call such a spectrum a vibrationally induced rotational spectrum, and have made a systematic examination of the point groups which permit such behaviour. We also give formulae for the approximate line frequencies and intensities in these spectra, and discuss some of the problems involved in observing them. The spectra can only arise from degenerate vibrational states, and are of three possible types: i) symmetric top perpendicular spectra, shown by molecules belonging to the point groups Dnh, Dn and Cnh, where n is odd; (ii) symmetric top parallel spectra, shown by molecules belonging to Dnd and S2n, where n is even; and (iii) spherical top spectra, shown by molecules belonging to T or Td. Excited vibrational states of polar molecules of point groups Cnv or Cn, where n is odd, may also possess vibrationally induced perpendicular components of type (i), in addition to their ordinary parallel spectra. In addition to the above limitations on the point groups there are, in general, limitations on the symmetry species of the degenerate vibrational states.

Microwave spectrum of CF3CCH

Attempts to observe ΔK = ±1 transitions in the rotational spectrum of CF3CCH and CF3H in the first excited state of a degenerate vibration, by direct absorption in the Y band and K band regions of the microwave spectrum, have not been successful. In the course of this work the J = 3-2 and 4-3 rotational spectrum of CF3CCH has been observed with higher sensitivity than previously, and from the positions of the vibrational satellites several new rB values have been determined.

Studies of pure rotational spectra of isolated molecules and molecular adducts using pulsed jet Fourier transform microwave (PJ-FTM) spectroscopy

This thesis focuses on studying molecular structure and internal dynamics by using pulsed jet Fourier transform microwave (PJ-FTMW) spectroscopy combined with theoretical calculations. Several kinds of interesting chemical problems are investigated by analyzing the MW spectra of the corresponding molecular systems. First, the general aspects of rotational spectroscopy are summarized, and then the basic theory on molecular rotation and experimental method are described briefly. ab initio and density function theory (DFT) calculations that used in this thesis to assist the assignment of rotational spectrum are also included. From chapter 3 to chapter 8, several molecular systems concerning different kind of general chemical problems are presented. In chapter 3, the conformation and internal motions of dimethyl sulfate are reported. The internal rotations of the two methyl groups split each rotational transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. In chapter 4 and 5, the results concerning two kinds of carboxylic acid bi-molecules, formed via two strong hydrogen bonds, are presented. This kind of adduct is interesting also because a double proton transfer can easily take place, connecting either two equivalent or two non-equivalent molecular conformations. Chapter 6 concerns a medium strong hydrogen bonded molecular complex of alcohol with ether. The dimer of ethanol-dimethylether was chosen as the model system for this purpose. Chapter 7 focuses on weak halogen…H hydrogen bond interaction. The nature of O-H…F and C-H…Cl interaction has been discussed through analyzing the rotational spectra of CH3CHClF/H2O. In chapter 8, two molecular complexes concerning the halogen bond interaction are presented.

Non-Covalent Interaction: Revealed by Rotational Spectroscopy

The pulsed jet Fourier transform microwave spectroscopy have been applied to several molecular complexes involving H2O, freons, methane, carboxylic acids, and rare gas. The obtained results showcase the suitability of this technique for studying the intermolecular interactions. The rotational spectra of three water adducts of halogenated organic molecules, i.e. chlorotrifluoroethylene, isoflurane and alfa,alfa,alfa,-trifluoroanisole, have been investigated. It has been found that, the halogenation of the partner molecules definitely changes the way in which water will link to the partner molecule. Quadrupole hyperfine structures and/or the tunneling splittings have been observed in the rotational spectra of difluoromethane-dichloromethane, chlorotrifluorometane-fluoromethane, difluoromethane-formaldehyde and trifluoromethane-benzene. These features have been useful to describe their intermolecular interactions (weak hydrogen bonds or halogen bonds), and to size the potential energy surfaces of their internal motions. The rotational spectrum of pyridine-methane pointed out that methane prefers to locate above the ring and link to pyridine through a C-H•••π weak hydrogen bond, rather than the C-H•••n interaction. This behavior, typical of complexes of pyridine with rare gases, suggests classifying CH4, in relation to its ability to form molecular complexes with aromatic molecules, as a pseudo rare gas. The conformational equilibria of three bi-molecules of carboxylic acids, acrylic acid-trifluoroacetic acid, difluoroacetic acid-formic acid and acrylic acid-fluoroacetic acid have been studied. The increase of the hydrogen bond length upon H→D isotopic substitution (Ubbelohde effect) has been deduced from the elongation of the carboxylic carbons C•••C distance. The van der Waals complex tetrahydrofuran-krypton shows that the systematic doubling of the rotational lines has been attributed to the residual pseudo-rotation of tetrahydrofuran in the complex, based on the values of the Coriolis coupling constants, and on the type (mu_b) of the interstate transitions.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (13C, 15N, 18O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)7, in both 2– 8 GHz and 6–18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to pro- vide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues (H218O and HDO), and a least-squares rm(1) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O–O equilibrium distances at the 0.01 Å level.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have changed the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (C-13, N-15, O-18) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2-8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)(7), in both 2-8 GHz and 6-18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to provide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues ((H2O)-O-18 and HDO), and a least-squares r(m)((1)) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O-O equilibrium distances at the 0.01 angstrom level. (C) 2013 Elsevier B.V. All rights reserved.

The nuclear electric quadrupole moment of hafnium from the molecular method

The molecular method is used to obtain nuclear electric quadrupole moment (NQM) values for hafnium through electric field gradients (EFGs) at this nucleus in HfO and HfS. Dirac-Coulomb calculations with the Coupled Cluster approach, DC-CCSD (T) and DC-CCSD-T, were carried out to achieve the most accurate estimates of these EFGs. Higher order corrections are also added. Hence, the most reliable values for 177Hf and 179Hf determined here are 3319(33) and 3750(37) mbarn, respectively, in nice accordance with the best currently accepted NQMs for this element. (C) 2012 Elsevier B.V. All rights reserved.

State-Selective Attachment of Helium to Molecular Ions in a New Cryogenic Ion Trap

Light is the main information about the interstellar medium accessible on Earth. Based on this information one can conclude on the composition of the region where the light originates from, as well as on its history. The requirement for this is that it is possible to identify the different absorption and emission features in the spectrum and assign them to certain molecules, atoms or ions. To enable the identification of the different species, precise spectroscopic investigations of the species in the laboratory are necessary. In this work a new spectroscopic method is presented, which can be used to record pure rotational spectra of mass selected, cold, stored molecular ions. It is based on the idea of state specific attachment of helium atoms to the stored molecular ions. The new technique has been made possible through the development and recent completion of two new 22-pole ion trap instruments in the work group of Laboratory Astrophysics at the University of Cologne. These new instruments have the advantage to reach temperatures as low as 4K compared to the 10K of the predecessor instrument. These low temperatures enable the ternary attachment of helium atoms to the stored molecular ions and by this make it possible to develop this new method for pure rotational spectroscopy. According to this, this work is divided into two parts. The first part deals with the new FELion experiment that was build and characterized in the first part of the thesis. FELion is a cryogenic 22-pole ion trap apparatus, allowing to generate, mass select, store and cool down, and analyze molecular ions. The different components of the instrument, e.g. the Storage Ion Source for generating the ions or the first quadrupole mass filter, are described and characterized in this part. Besides this also the newly developed control and data acquisitions system is introduced. With this instrument the measurements presented in the second part of the work were performed. The second part deals with the new action spectroscopic method of state-selective helium attachment to the stored molecular ions. For a deeper analysis of the new technique the systems of CD+ and helium and HCO+ and helium are investigated in detail. Analytical and numerical models of the process are presented and compared to experimental results. The results of these investigations point to a seemingly very general applicability of the new method to a wide class of molecular ions. In the final part of the thesis measurements of the rotational spectrum of l-C3H+ are presented. These measurements have to be high-lighted, since it was possible for the first time in the laboratory to unambiguously measure four low-lying rotational transitions of l-C3H+. These measurements (Brünken et al. ApJL 783, L4 (2014)) enabled the reliable identification of so far unidentified emision lines observed in several regions of the interstellar medium (Pety et al. Astron. Astrophys. 548, A68 (2012), McGuire et al. The Astrophysical Journal 774, 56 (2013) and McGuire et al. The Astrophysical Journal 783, 36 (2014)).

Design, construction, and applications of a high-resolution terahertz time-domain spectrometer

This thesis reports on the design, construction, and initial applications of a high-resolution terahertz time-domain ASOPS spectrometer. The instrument employs asynchronous optical sampling (ASOPS) between two Ti:sapphire ultrafast lasers operating at a repetition rate of approximately 80 MHz, and we thus demonstrate a THz frequency resolution approaching the limit of that repetition rate. This is an order of magnitude improvement in resolution over typical THz time-domain spectrometers. The improved resolution is important for our primary effort of collecting THz spectra for far-infrared astronomy. We report on various spectroscopic applications including the THz rotational spectrum of water, where we achieve a mean frequency error, relative to established line centers, of 27.0 MHz. We also demonstrate application of the THz system to the long-duration observation of a coherent magnon mode in a anti-ferromagnetic yttrium iron oxide (YFeO3) crystal. Furthermore, we apply the all-optical virtual delay line of ASOPS to a transient thermoreflectance experiment for quickly measuring the thermal conductivity of semiconductors.

High resolution optogalvanic spectrum of N2-rotational structure of (11, 7) band in the first positive system

High resolution optogalvanic spectrum of the (11, 7) band in the first positive system of nitrogen molecule has been recorded from 17179 to 17376 cm- 1. Assignment of 432 rotational lines belonging to the 27 branches of this band has been carried out.

Rotational isomerism about the Ca-CO bond in proline derivatives. 1H and 13C NMR studies of benzyloxycarbonyl-Pro-N-methylamide and pivaloyl-Pro-N-methylamide

The 270 MHz 1H n.m.r. spectrum of benzyloxycarbonyl-Pro-N-methylamide in CDCl3 is exchange broadened at 293° K. Spectral lines due to two species are frozen out at 253° K and a dynamically averaged spectrum is obtained at 323° K. A selective broadening of the Cβ and Cγ resonances in the 13C n.m.r. spectrum is observed at 253° K, with a splitting of the Cβ and Cγ resonances into a pair of lines of unequal intensity. A similar broadening of Cβ and Cγ peaks is also detected in pivaloyl-Pro-N-methylamide where cis-trans interconversion about the imide bond is precluded by the bulky t-butyl group. The rate process is thus attributed to rotation about the Cα-CO bond (ψ) and a barrier (ΔG#) of 14kcal mol-1 is estimated. 13C n.m.r. data for pivaloyl-Pro-N-methylamide in a number of solvents is presented and the differences in the Cβ and Cγ chemical shifts are interpreted in terms of rotational isomerism about the Cα-CO bond.

Raman spectrum of ethyl chloroacetate

The Raman spectrum of ethyl chloroacetate has been studied at 13° C., 28° C. and 78° C. The carbonyl frequency was found to be split up into two due to the presence of rotational isomers. The higher frequency line due to thecis isomer was found to decrease in intensity with temperature. It appears that the gauche isomer will predominate in the vapour state. Altogether thirty-eight Raman lines have been recorded. Reasonable assignments for the observed Raman lines were made in comparison with ethyl acetate spectrum.

Microwave spectrum and structure of C(6)H(5)CCH center dot center dot center dot H(2)S complex

Rotational spectra of C(6)H(5)CCH center dot center dot center dot H(2)S, C(6)H(5)CCH center dot center dot center dot H(2)(34)S, C(6)H(5)CCH center dot center dot center dot HDS, C(6)H(5)CCH center dot center dot center dot D(2)S and C(6) H(5)CCD center dot center dot center dot H(2)S complexes have been observed using a pulsed nozzle Fourier transform microwave spectrometer. The observed spectrum is consistent with a structure in which hydrogen sulfide is located over the phenyl ring pi cloud and the distance between the centers of masses of the two monomers is 3.74 +/- 0.01 angstrom. In the complex, the H(2)S unit is shifted from the phenyl ring center towards the acetylene group. The vibrationally averaged structure has an effective Cs symmetry. Ab initio calculations were performed at MP2/aug-cc-pVDZ level of theory to locate the possible geometries of the complex. The calculations reveal the experimentally observed structure to be more stable than a coplanar arrangement of the monomers, which was observed for the C(6)H(5)CCH center dot center dot center dot H(2)O complex. Atoms in molecule theoretical analysis shows the presence of S-H center dot center dot center dot pi hydrogen bond. For the parent isotopologue, each transition frequency was found to split into two resulting from an interchange of the equivalent hydrogens of H(2)S unit in the complex. (C) 2011 Elsevier Inc. All rights reserved.

Microwave Spectrum of Hexafluoroisopropanol and Torsional Behavior of Molecules with a CF3-C-CF3 Group

This paper presents the first microwave spectroscopic investigation on hexafluoroisopropanol (HFIP). A pulsed nozzle Fourier transform microwave spectrometer has been used to determine the rotational constants for HFIP as A = 2105.12166(18) MHz, B = 1053.99503(12) MHz, and C = 932.33959(13) MHz. In addition, five isotopologues of HFIP have been observed experimentally to determine the accurate structure of HFIP. The observed spectrum could be assigned to the most stable conformer of HFIP, called antiperiplanar. Available spectroscopic information and ab initio calculations on five prototype molecules helped in exploring the torsional behavior of molecules having a CF3-C-CF3 group. Two-dimensional potential energy surfaces have been analyzed for all molecules, which explained the presence/absence of doubling in the rotational transitions. With the help of natural bond orbital (NBO) analysis, reasons for the conformational preference of HFIP have been explained.

The VLT-FLAMES survey of massive stars: stellar parameters and rotational velocities in NGC 3293, NGC 4755 and NGC 6611

An analysis is presented of VLT-FLAMES spectroscopy for three Galactic clusters, NGC3293, NGC4755 and NGC6611. Non-LTE model atmosphere calculations have been used to estimate effective temperatures (from either the helium spectrum or the silicon ionization equilibrium) and gravities (from the hydrogen spectrum). Projected rotational velocities have been deduced from the helium spectrum (for fast and moderate rotators) or the metal line spectrum (for slow rotators). The origin of the low gravity estimates for apparently near main sequence objects is discussed and is related to the stellar rotational velocity. The atmospheric parameters have been used to estimate cluster distances (which are generally in good agreement with previous determinations) and these have been used to estimate stellar luminosities and evolutionary masses. The observed Hertzsprung-Russell diagrams are compared with theoretical predictions and some discrepancies including differences in the main sequence luminosities are discussed. Cluster ages have been deduced and evidence for non-coeval star formation is found for all three of the clusters. Projected rotational velocities for targets in the older clusters, NGC3293 and NGC4755, have been found to be systematically larger than those for the field, confirming recent results in other similar age clusters. The distribution of projected rotational velocities are consistent with a Gaussian distribution of intrinsic rotational velocities. For the relatively unevolved targets in the older clusters, NGC3293 and NGC4755, the peak of the velocity distribution would be 250 km s(-1) with a full-width-half-maximum of approximately 180 km s(-1). For NGC6611, the sample size is relatively small but implies a lower mean rotational velocity. This may be evidence for the spin-down effect due to angular momentum loss through stellar winds, although our results are consistent with those found for very young high mass stars. For all three clusters we deduce present day mass functions with Gamma-values in the range of -1.5 to -1.8, which are similar to other young stellar clusters in the Milky Way.