G. Grubbs

A Study of the Monohydrate and Dihydrate Complexes of Perfluoropropionic Acid Using Chirped-Pulse Fourier Transform Microwave (CP-FTMW) Spectroscopy.

This work reports the first known spectroscopic observation of the monohydrate and dihydrate complexes of perfluoropropionic acid (PFPA). The spectra have been observed using a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer in the 7750 to 14,250 MHz region. The structures of the species have been confirmed with the aid of ab initio quantum chemical calculations. Rotational constants A, B, and C have been determined and reported for both species along with centrifugal distortion constants ΔJ, ΔJK, ΔK, δJ, δK for H2O-PFPA and ΔJ, ΔJK, and δJ for (H2O)2-PFPA. Effects due to large amplitude motions were not observable in these experiments. Structures of the complexes have been determined using a combination of experimental second moment values and ab initio results. The complexation of the -OH of one or two water molecules has been found to occur in the plane of the carboxylic acid group forming a six- or eight-member ring.

THE COMPLETE HEAVY-ATOM STRUCTURE OF A CP-FTMW CHIRAL TAG PRECURSOR, VERBENONE

FRANK E MARSHALL, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA; CHANNING WEST, GALEN SEDO, Department of Natural Sciences, University of Virginia’s College at Wise, Wise, VA, USA; BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA; G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.

AN INVESTIGATION OF THE DIPOLE FORBIDDEN TRANSITION EFFECTS IN BROMOFLUOROCARBONS AS IT PERTAINS TO 3-BROMO-1,1,1,2,2-PENTAFLUOROPROPANE USING CP-FTMW SPECTROSCOPY

As part of a series of bromofluorocarbon species and analogues, the microwave spectrum of the molecule 3-bromo-1,1,1,2,2-pentafluoropropane has been measured on a CPFTMW spectrometer located at Missouri S&T. The resultant spectrum is dense with transitions occurring at a rate of ≈1 transition/MHz! Within the spectrum, Br and Br isotopologues of multiple conformers of 3-bromo-1,1,1,2,2-pentafluoropropane have been identified. Rotational constants, centrifugal distortion parameters, nuclear quadrupole coupling constants and how each compare with theory for each conformer will be discussed. Due to the large quadrupolar moment of bromine, heavy, brominated molecules are good candidates for dipole-forbidden transitions. Previous studies with bromoperfluoroacetonea provided a rich spectrum full of dipole forbidden transitions that 3-bromo-1,1,1,2,2-pentafluoropropane does not share. This difference will be explained using structural considerations along with the matrix elements needed to enact these transitions.

A CHIRPED PULSE FOURIER TRANSFORM MICROWAVE (CP-FTMW) SPECTROMETER WITH LASER ABLATION SOURCE TO SEARCH FOR ACTINIDE-CONTAINING MOLECULES AND NOBLE METAL CLUSTERS

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.ab 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.

THE CP-FTMW SPECTROSCOPY AND ASSIGNMENT OF THE MONO- AND DIHYDRATE COMPLEXES OF PERFLUOROPROPIONIC ACID

G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA; DANIEL A. OBENCHAIN, DEREK S. FRANK, STEWART E. NOVICK, Department of Chemistry, Wesleyan University, Middletown, CT, USA; S. A. COOKE, Natural and Social Science, Purchase College SUNY, Purchase, NY, USA; AGAPITO SERRATO III, WEI LIN, Department of Chemistry, University of Texas, Brownsville, TX, USA.

A SIMPLE, COST EFFECTIVE RAMAN-FLUORESCENCE SPECTROMETER FOR USE IN LABORATORY AND FIELD EXPERIMENTS

FRANK E MARSHALL, MICHAEL A PRIDE, MICHELLLE ROJO, KATELYN R. BRINKER, ZACHARY WALKER, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA; MICHAEL STORRIE-LOMBARDI, Department of Physics, Harvey Mudd College and Kinohi Institute, Inc., Claremont, CA, USA; MELANIE R. MORMILE, Department of Biological Sciences, Missouri University of Science and Technology, Rolla, MO, USA; G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.