The microwave spectrum of methyl butanoate has been taken from 8-18 GHz using a chirped pulse spectrometer. This molecule is a model biofuel, and its thermal decomposition products are of interest due to its many dissociation channels. As a preliminary step before such pyrolysis studies, we have examined the jet cooled spectrum of methyl butanoate in a chirped pulse spectrometer, which shows a very rich spectrum. Several conformers have been identified, each with tunneling splittings in the methyl ester group due to internal rotation. These spectra have been fit to obtain rotational constants, relative populations, and methyl rotor barriers for each conformational isomer. The results of these studies are compared to high level calculations.

Benzocaine (BZ), butamben (BTN) and isobutamben (BTI) are local anesthetics characterized by a hydrophilic head and a lipophilic aliphatic tail linked by an aminobenzoate group. Previous rotational work on BZ (H₂N-C₆H₄-COO-Et)A. Lesarri, S. T. Shipman, G. G. Brown, L. Alvarez-Valtierra, R. D. Suenram, B. H. Pate, Int. Symp. Mol. Spectrosc., 2008, Comm. RH07.howed that its ethyl aliphatic tail may adopt either in-plane (trans) or out of plane (gauche) conformations, with a low interconversion barrier below 50 cm⁻¹.E. Aguado, A. Longarte, E. Alejandro, J. A. Fernández, F. Castaño, J. Phys. Chem. A, 2006, 110, 6010.ere we extend the rotational study to BTN and BTI, isolated in a supersonic jet expansion and vaporized either by heating or UV ps-laser ablation methods. Both molecules share a 14 heavy-atoms skeleton, differing in their butyl (-(CH₂)₃-CH₃) or isobutyl (-CH₂-CH(CH₃)₂) four-carbon tail. We detected a single conformer for BTN and two conformers for BTI. The two molecules do not adopt an all-trans carbon skeleton. Conversely, the β-ethyl carbon in BTN is gauche. For BTI the β-carbon may be either trans or gauche. The microwave spectrum covered the cm- (BTN, BTI, 6-18 GHz) and mm-wave (BTW, 50-75 GHz) frequency ranges.In all the cases, rotational and centrifugal distortion constants as well as the diagonal elements of the ¹⁴N nuclear quadrupole coupling tensor were accurate determined and compared to the theoretical results (ab initio and DFT). No transitions belonging to configurations predicted as higher minima of the PES were found, pointing out that conformational interconversions may take place in the jet.

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A. Lesarri, S. T. Shipman, G. G. Brown, L. Alvarez-Valtierra, R. D. Suenram, B. H. Pate, Int. Symp. Mol. Spectrosc., 2008, Comm. RH07.s E. Aguado, A. Longarte, E. Alejandro, J. A. Fernández, F. Castaño, J. Phys. Chem. A, 2006, 110, 6010.H

r0pt Figure The pure rotational spectra of the n = 5, 6, 7, and 8 members of the 1-fluoroalkane family have been recorded between 7 GHz and 14 GHz using chirped pulse Fourier transform microwave spectroscopy. The spectra have been analyzed and results will be presented and compared with previous work on the n= 2, 3, and 4 membersM. Hayashi, M. Fujitake, T. Inagusa, S. Miyazaki, J.Mol.Struct., 216, 9-26, 1990 ; W. Caminati, A. C. Fantoni, F. Manescalchi, F. Scappini, Mol.Phys., 64, 1089 ,1988 ; L. B. Favero, A. Maris, A. Degli Esposti, P. G. Favero, W. Caminati, G. Pawelke, Chem.Eur.J., 6(16), 3018-3025, 2000 The lowest energy conformer for all family members has the common feature that the fluorine is in a gauche position relative to the alkyl tail for which all other heavy atom dihedral angles, where appropriate, are 180 degrees. For the n = 3 and higher family members the second lowest energy conformer has all heavy atom dihedral angles equal to 180 degrees. For each family member transitions carried by both low energy conformers were observed in the collected rotational spectra. Quantum chemical calculations were performed and trends in the energy separations between these two common conformers will be presented as a function of chain length. Furthermore, longer chain lengths have been examined using only quantum chemical calculations and results will be presented.

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M. Hayashi, M. Fujitake, T. Inagusa, S. Miyazaki, J.Mol.Struct., 216, 9-26, 1990 ; W. Caminati, A. C. Fantoni, F. Manescalchi, F. Scappini, Mol.Phys., 64, 1089 ,1988 ; L. B. Favero, A. Maris, A. Degli Esposti, P. G. Favero, W. Caminati, G. Pawelke, Chem.Eur.J., 6(16), 3018-3025, 2000 .

Fourier transform molecular rotational resonance spectroscopy (FT-MRR) using pulsed jet molecular beam sources is a high-resolution spectroscopy technique that can be used for chiral analysis of molecules with multiple chiral centers. The sensitivity of the molecular rotational spectrum pattern to small changes in the three dimensional structure makes it possible to identify diastereomers without prior chemical separation. For larger molecules, there is the additional challenge that different conformations of each diastereomer may be present and these need to be differentiated from the diastereomers in the spectral analysis. Broadband rotational spectra of several larger molecules have been measured using a chirped-pulse FT-MRR spectrometer. Measurements of nootkatone (C₁₅H₂₂O), cedrol (C₁₅H₂₆O), ambroxide (C₁₆H₂₈O) and sclareolide (C₁₆H₂₆O₂) are presented. These spectra are measured with high sensitivity (signal-to-noise ratio near 1,000:1) and permit structure determination of the most populated isomers using isotopic analysis of the ¹³C and ¹⁸O isotopologues in natural abundance. The accuracy of quantum chemistry calculations to identify diastereomers and conformers and to predict the dipole moment properties needed for three wave mixing measurements is examined.

Chiral analysis on molecules with multiple chiral centers can be performed using pulsed-jet Fourier transform rotational spectroscopy. This analysis includes quantitative measurement of diastereomer products and, with the three wave mixing methods developed by Patterson, Schnell, and Doyle (Nature 497, 475-477 (2013)), quantitative determination of the enantiomeric excess of each diastereomer. The high resolution features enable to perform the analysis directly on complex samples without the need for chromatographic separation. Isopulegol has been chosen to show the capabilities of Fourier transform rotational spectroscopy for chiral analysis. Broadband rotational spectroscopy produces spectra with signal-to-noise ratio exceeding 1000:1. The ability to identify low-abundance (0.1-1%) diastereomers in the sample will be described. Methods to rapidly identify rotational spectra from isotopologues at natural abundance will be shown and the molecular structures obtained from this analysis will be compared to theory. The role that quantum chemistry calculations play in identifying structural minima and estimating their spectroscopic properties to aid spectral analysis will be described. Finally, the implementation of three wave mixing techniques to measure the enantiomeric excess of each diastereomer and determine the absolute configuration of the enantiomer in excess will be described.

Rotational spectra of Tetrahydro-2-furoic acid (THA), a chiral acid, and its homo- and heterochiral dimers, and its complex with water have been recorded using a chirped pulse Fourier transform microwave spectrometer. This chiral acid was predicted to have nine conformers, although only the most stable one was detected experimentally and its rotational spectrum assigned. We have analyzed its intramolecular H-bonding pattern in detail. Eleven conformers have been predicted for the 1:1 hydration complex between THA and water and 14 conformers for (THA)₂. The assignments of these complexes are currently underway and will be presented.

Polyethylene oxides (Polyethylene glycoles) and their phenoxy-capped analogs represent a prominent class of important polymers that are highly used as precursor molecules in supramolecular reactions. After a detailed study on the simplest representative (1,2-dimethoxyethane) [1], we present results on oligoethylene oxides with increasing chain lengths obtained by spontaneous Raman scattering in a supersonic jet. Through variation of stagnation pressure, carrier gas, nozzle distance and temperature we gain information on the conformational landscape as well as the mutual interconversion of low energy conformers. The obtained results are compared to state-of-the-art quantum chemical calculations. Additionally, we present UV as well as IR-UV and UV-UV double resonance studies on 1-methoxy-2-phenoxyethane in a supersonic jet. These complementary techniques allow for conformationally selective electronic and vibrational spectra in a closely related conformational landscape. [1] S. Bocklitz, M. A. Suhm, Constraining the Conformational Landscape of a Polyether Building Block by Raman Jet Spectroscopy, Z. Phys. Chem. 2015, 229, 1625-1648.

Conformation-specific UV-IR double resonance spectra are presented for n-alkylbenzenes. With the aid of a local mode Hamiltonian that includes the effects of stretch-bend Fermi coupling, the spectra of ethyl, n-propyl, and n-butylbenzene are assigned to individual conformers. These molecules allow for further development of the work on a first principles method for calculating alkyl stretch spectra. Due to the consistency of the anharmonic couplings from conformer to conformer, construction of the model Hamiltonian for a given conformer only requires a harmonic frequency calculation at the conformer's minimum geometry as an input. The model Hamiltonian can be parameterized with either density functional theory or MP2 electronic structure calculations. The relative strengths and weaknesses of these methods are evaluated, including their predictions of the relative energetics of the conformers. Finally, the IR spectra for conformers that have the alkyl chain bend back and interact with the π cloud of the benzene ring are modeled.

Alkylbenzenes make up 20-30% of petroleum fuels and are important intermediates in combustion. In gasoline, these alkyl chains are relatively short, but extend to 20 or more carbons in length in diesel fuels. While one tends to think of these chains as extending out away from the phenyl ring in an all-trans configuration, dispersive interactions between segments of the alkyl chain and between the alkyl chain and the ring will stabilize more compact geometries in which the alkyl chain folds back on itself and extends over the aromatic π cloud. This talk seeks to answer the following question: How long must the alkyl chain be before it starts to fold back over itself? Studies of the pure n-alkanes by the Suhm group have shown the turn to favorably occur for a chain about 17 carbon atoms in length. The studies presented here focus on the affect the aromatic ring has on when this turn becomes favorable. Jet-cooled laser-induced fluorescence excitation and single-conformation IR spectra have been recorded in the alkyl CH stretch region for a series of alkylbenzenes with chain lengths ranging from two to ten carbon atoms. We show, through a combination of experiment, high level calculation, and theoretical modeling, that conformations begin to form that fold back over the aromatic ring at about n=8.

The non-resonant interaction of electromagnetic radiation with an isotropic ensemble of chiral molecules, which causes the incident state of linear polarization to undergo a signed rotation, long has served as a metric for gauging the enantiomeric purity of asymmetric syntheses. While the underlying phenomenon of circular birefringence (CB) typically is probed in the condensed phase, recent advances in ultrasensitive circular-differential detection schemes, as exemplified by the techniques of Cavity Ring-Down Polarimetry (CRDP), have permitted the first quantitative analyses of such processes to be performed in rarefied media. Efforts to extend vapor-phase investigations of CB to new families of chiral substrates will be discussed, with particular emphasis directed towards the elucidation of intrinsic (e.g., solvent-free) properties and their mediation by environmental perturbations (e.g., solvation). Specific species targeted by this work will include the stereoselective building blocks phenylpropylene oxide and α-methylbenzyl amine, both of which exhibit pronounced solvent-dependent changes in measured optical activity. The nature of chiroptical response in different environments will be highlighted, with quantum-chemical calculations serving to unravel the structural and electronic provenance of observed behavior.

Emission spectra provide us with rich information about the excited-state processes such as proton-transfer, charge-transfer and so on. In the cases that more than one excited states are involved, emission spectra from different excited states sometimes overlap and a decomposition of the overlapped spectra is desired. One of the methods to perform a decomposition is a time-resolved fluorescence technique. It uses a difference in time evolutions of components involved. However, in the gas-phase, a concentration of the sample is frequently too small to carry out this method. On the other hand, double-resonance technique is a very powerful tool to discriminate or identify a common species in the spectra in the gas-phase. Thus, in the present study, we applied the double-resonance technique to resolve the overlapped emission spectra. When transient IR absorption spectra of the excited state are available, we can label the population of the certain species by the IR excitation with a proper selection of the IR wavenumbers. Thus, we can obtain the emission spectra of labeled species by subtracting the emission spectra with IR labeling from that without IR. In the present study, we chose the charge-transfer emission spectra of cyanophenyldisilane (CPDS) as a test system. One of us reported that two charge-transfer (CT) states are involved in the intramolecular charge-transfer (ICT) process of CPDS-water cluster and recorded the transient IR spectraH. Ishikawa, et al., Chem. Phys. Phys. Chem., 9, 117 (2007). As expected, we have succeeded in resolving the CT emission spectra of CPDS-water cluster by the double resonance facilitated decomposion technique. In the present paper, we will report the details of the experimental scheme and the results of the decomposition of the emission spectra.

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H. Ishikawa, et al., Chem. Phys. Phys. Chem., 9, 117 (2007). .

r0.25 Figure Microwave spectroscopic techniques have traditionally been part of the foundation of molecular structure and this conference. Instrumental developments by Brooks Pate and sourcing developments by Steve Cooke on these instruments have allowed for the dawning of a new era in modern microwave spectroscopic techniques.G. G. Brown, B. C. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman, B. H. Pate, Rev. Sci. Instrum. 79 (2008) 053103-1 – 053103-13.G. S. Grubbs II, C. T. Dewberry, K. C. Etchison, K. E. Kerr, S. A. Cooke, Rev. Sci. Instrum. 78 (2007) 096106-1 – 096106-3. With these advances and the growth of powerful computational approaches, microwave spectroscopists can now search for molecules and/or cluster systems of actinide and noble metal-containing species with increasing certainty in molecular assignment even with the difficulties presented with spin-orbit coupling and relativistic effects. Spectrometer and ablation design will be presented along with any preliminary results on actinide-containing molecules or noble metal clusters or interactions.

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G. G. Brown, B. C. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman, B. H. Pate, Rev. Sci. Instrum. 79 (2008) 053103-1 – 053103-13.

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r0pt Figure The thermal decomposition of cyclohexanone (C₆H₁₀=O) has been studied in a set of flash-pyrolysis micro-reactors. Samples of C₆H₁₀=O were first observed to decompose at 1200 K. Short residence times of 100 μsec and dilution of samples ( < 0.1%) isolate unimolecular decomposition. Products were identified by tunable VUV photoionization mass spectroscopy, photoionization appearance thresholds, and complementary matrix infrared absorption spectroscopy. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways pictured to the right. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C₆H₉OH), is followed by retro-Diels-Alder cleavage to CH₂=CH₂ and CH₂=C(OH)-CH=CH₂. Further isomerization of CH₂=C(OH)CH=CH₂ to methyl vinyl ketone (CH₃COCH=CH₂, MVK) was also observed. Photoionization spectra identified both enols, C₆H₉OH and CH=C(OH)CH=CH₂, and the ionization threshold of C₆H₉OH was measured to be 8.2 ± 0.1 eV. At 1200 K, the products of cyclohexanone pyrolysis were found to be: C₆H₉OH, CH₂=C(OH)CH=CH₂, MVK, CH₂CHCH₂, CO, CH₂=C=O, CH₃, CH₂=C=CH₂, CH₂=CH-CH=CH₂, CH₂=CHCH₂CH₃, CH₂=CH₂, and HCCH.

The traditional spectroscopic methods to measure enantiomeric excess, based upon optical rotation or circular dichroism arise from an interference of electric and magnetic dipole contributions of an optical transitions. The later is relativisitic and gets smaller with decreasing frequency and thus these effects have not been previously observed in pure rotational spectroscopy. First introduced by the group at Harvard¹, it is possible to use a 3-wave mixing method (with one of the fields potentially a Stark Field) to distinguish enantiomers if the three wave are nonplaner. In the conceptually simplest form of this experiment, a molecule is polarized with X polarization on a a → b transition, and then the resulting ρ_ab molecular coherence is transferred to a ρ_ac coherence by application of a π pulse on the b → c transition. For a chiral molecule with nonzero dipole projections on the three inertial axes, this ρ_ac coherence can radiate Z polarized emission at the frequency of the a → c transition. In this talk, I will present the full theory of such experiments, including accounting for dirrection cosine matrix elements and M degeneracy. The resulting expressions can be used to calculate the expected size of the signal as a function of the specific transitions used in the a → b → c → a cycle.² It will be demonstrated that the maximum size of the ρ_ac coherence is nearly that generated by a "π/2’’ pulse on the a → c transition. However, it is not possible to phase match the emission generated by this polarization due to the requirement that the three fields be orthogonal. Given that in rotational spectroscopy the physical size of the sample produced in a pulsed supersonic jet is comparable to the wavelengths of the microwave fields, the lack of phase matching produces a substantial but not catastrophic loss in the amplitude of the emitted free induction decay field. I will present a proposal to realize an analogy of quasiphase matching to ameliorate the dephasing. 1. D. Patterson, M. Schnell, & JM Doyle, Nature 497, 475 (2013); D Patterson & JM Doyle, PRL 111, 023008 (2013) 2. S. Lobsiger et al, JCPL 6, 196 (2015).

Microwave three-wave mixing spectroscopy produces a Free Induction Decay Field that is proportional to the enantiomeric excess ( ee ) of a sample of chiral molecules. However, since there is an unavoidable loss of measured signal strength due to dephasing of the molecular emission, it is not possible to quantitate this ee unless one has an enantiomeric pure sample of the same molecule with which to compare the amplitude of the signal of a sample of unknown ee. In this talk, I will demonstrate that it is in principle possible to use a 5 wave mixing experiment, based upon AC Stark shifts produced by nearly resonant fields, to produce a differential splitting of a transition such that one has frequency resolved peaks for the two enantiomers. The peaks corresponding to the two enantiomers can be switched by phase cycling of the fields. This method is promising to allow the quantitative measurement of molecular ee’s by microwave spectroscopy. There are experimental issues that make such an experiment difficult. It will likely be required to use of skimmed molecular beam (which will substantially reduce the number of molecular emitters and thus signal level) in order to reduce the field amplitude and phase inhomogeneity of the excited molecules.