Fourier Transform Microwave Spectrum and ab Initio Study of Dimethyl Methylphosphonate

Suenram, R. D.; Lovas, Francis J.; Plusquellic, David F.; Lesarri, Alberto; Kawashima, Yasunaru; Jensen, James O.; Samuels, Alan C.

doi:10.1006/jmsp.2001.8486

Cited by 75 publications

(118 citation statements)

References 10 publications

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“…The molecular jet is produced using a pulsed circular (1-mm diameter) nozzle from General Valve Series 9 model, controlled by a valve driver (Iota One, Parker Hannifin). MTO is seeded in the supersonic jet using a brass reservoir heated to 370 K (after a design from NIST 23 and PhLAM 24 ). The reservoir is filled with 0.5 g of MTO powder, and the sublimated vapour is swept away by argon at a backing pressure of 1.2 bar.…”

Section: Ii-2-1-b the Vacuum System And Supersonic Jetmentioning

confidence: 99%

Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements

Asselin

Berger

Huet

et al. 2017

Phys. Chem. Chem. Phys.

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Following our first paper about high resolution spectroscopy of methyltrioxorhenium (MTO) [Stoeffler et al. PCCP, 13, 854, (2011)], the present study reports a deeper investigation of the ground state, and Re=O antisymmetric (as) and symmetric (s) stretching excited states of both CH3 187 ReO3 and CH3 185 ReO3 isotopologues, thanks to new devices implemented within our consortium. We carry out high resolution millimeter-wave (MMW) and infrared (IR) spectroscopy in room temperature absorption cells, in a pulsed supersonic jet and in a cryogenic buffer gas cell. This collection of sensitive spectrometers enables us to probe both levels of a vibrational transition in low and room temperature gaseous environments. We thus report a new series of measurements providing particularly accurate rotational and rovibrational data for such a large and heavy organometallic molecule that is solid at room temperature.The combination of the new MMW and IR data leads to an improvement of the rovibrational model of MTO: (i) rotational spectra are extended to the 150-300 GHz range and are analyzed to characterize the ground state rotational and hyperfine structure up to J = 43 and K = 41, resulting in the significant refinement of rotational, quartic and hyperfine parameters, as well as the determination of sextic parameters and a centrifugal distortion correction to the quadrupolar hyperfine constant,(ii) rovibrational data recorded at very different temperatures (between 6 and 300 K) in the 970-1015 cm -1 range, at resolutions down to 8 MHz and frequency accuracies as high as 30 MHz (using the buffer gas technique), are used in a first step to extract more precise excited-state rotational, Coriolis and quartic parameters as well as the ground-state centrifugal distortion parameter of the 187 Re isotopologue, which isn't accessible from rotational spectroscopy alone. In a second step, taking the hyperfine structure into account, the upper state rhenium atom quadrupole coupling constant eQq' is determined from the assignment of partially hyperfine-resolved CO2 laser absorption spectra of a skimmed molecular beam.* now at National Physical Laboratory, Teddington, TW11 0LW, UK. 2 IIntroductionThere is an increasing demand for precision spectroscopy of polyatomic molecules. For example, precise knowledge of molecular constants is required for modeling atmospheres, whether it be our own 1,2 or those found in exo-planets 3 and in the interstellar medium 4 , for studying collision physics 5,6 , and as crucial groundwork for performing fundamental physics tests 7,8,9,10,11,12,13,14,15,16,17 . One such test is the measurement of the parity-violating (PV) energy difference between opposite enantiomers of a chiral molecule, induced by the weak interaction. 18 The chiral derivatives of methyltrioxorhenium (MTO) are excellent candidate species for this measurement, because calculations predict relatively large PV energy differences, and because it is possible to synthesize these molecules and bring them into the gas phase. 8,17,19,20 In...

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Section: Ii-2-1-b the Vacuum System And Supersonic Jetmentioning

confidence: 99%

Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements

Asselin

Berger

Huet

et al. 2017

Phys. Chem. Chem. Phys.

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“…[1] and [2] and the approximate equilibrium values for the structural parameters given in Table 7 and Eqs. [3] will be called framework 1 in this paper.…”

Section: Coordinate Systemmentioning

confidence: 99%

“…Atom positions of the intermediate configuration in the x y z axis system are just those from Eqs. [1] translated to a centerof-mass system; i.e., [4] where A (α a , α b , β d , β e ) is the center of mass of DMMP calculated from the a i (α a , α b , β d , β e ) positions given in Eqs. [1].…”

Section: Coordinate Systemmentioning

confidence: 99%

“…The chemical and other motivations for this work on dimethyl methylphosphonate (DMMP) are described in the companion paper (1), to which the reader is referred for additional introductory material, experimental information, ab initio results (see Fig. 2 of Ref.…”

Section: Introductionmentioning

confidence: 99%

“…2 of Ref. (1) for the ab initio molecular geometry), and spectral analyses, including an asymmetric rotor fit to experimental measurement precision of all assigned transitions involving tunneling components of A 1 and A 2 symmetry species. An additional theoretical motivation here is the desire to treat the three (or four) large-amplitude tunneling motions of DMMP quantitatively.…”

Section: Introductionmentioning

confidence: 99%

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Application of Permutation–Inversion Group Theory to the Interpretation of the Microwave Absorption Spectrum of Dimethyl Methylphosphonate

Ohashi

Hougen

2002

Journal of Molecular Spectroscopy

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The Conformational Landscape of Nicotinoids: Solving the Conformational Disparity of Anabasine

Lesarri

Cocinero

Evangelisti

et al. 2010

Chemistry A European J

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The conformational landscape of the alkaloid anabasine (neonicotine) has been investigated by using rotational spectroscopy and ab initio calculations. The results allow a detailed comparison of the structural properties of the prototype piperidinic and pyrrolidinic nicotinoids (anabasine vs. nicotine). Anabasine adopts two most stable conformations in isolation conditions, for which we determined accurate rotational and nuclear quadrupole coupling parameters. The preferred conformations are characterized by an equatorial pyridine moiety and additional N-H equatorial stereochemistry at the piperidine ring (eq-eq; eq=equatorial). The two rings of anabasine are close to a bisecting arrangement, with the observed conformations differing by an approximately 180 degrees rotation of the pyridine subunit, denoted either syn or anti. The preference of anabasine for the eq-eq-syn conformation has been established by relative intensity measurements (syn/anti approximately 5(2)). The conformational preferences of free anabasine are directed by a weak N...H-C hydrogen bond interaction between the nitrogen lone pair at piperidine and the closest C-H bond in pyridine, with N...H distances ranging from 2.686 (syn) to 2.667 A (anti). Supporting ab initio calculations by using MP2 and the recent M05-2X density functional are provided, evaluating the predictive performance of both methods.

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Fourier Transform Microwave Spectrum and ab Initio Study of Dimethyl Methylphosphonate

Cited by 75 publications

References 10 publications

Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements

Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements

Application of Permutation–Inversion Group Theory to the Interpretation of the Microwave Absorption Spectrum of Dimethyl Methylphosphonate

The Conformational Landscape of Nicotinoids: Solving the Conformational Disparity of Anabasine

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