σ-Hole activation and structural changes upon perfluorination of aryl halides: direct evidence from gas phase rotational spectroscopy.

Enhancement of the σ-hole on the halogen atom of aryl halides due to perfluorination of the ring is demonstrated by use of the Extended Townes-Dailey (ETD) model coupled to a Natural Atomic Orbital Bond analysis on two perfluorinated aryl halides (CFCl and CFBr) and their hydrogenated counterparts. The ETD analysis, which quantifies the halogen p-orbitals populations, relies on the nuclear quadrupole coupling constants which in this work are accurately determined experimentally from the rotational spectra. The rotational spectra investigated by Fourier-transform microwave spectroscopy performed in supersonic expansion are reported for the parent species of CFCl and CFBr and their C, Cl or Br substituted isotopologues observed in natural abundance.

Clozapine Reduces Self-Injurious Behavior in a State Prison Population.

Self-injurious behavior (SIB) is a common, disruptive, and costly occurrence in U.S. prisons.

Microwave Spectra and Structure of Ar-1,3-Difluorobenzene.

The microwave spectrum of the dimer Ar-1,3-difluorobenzene from 2 to 18 GHz is reported. The spectrum has been observed using a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer that has recently been expanded to include the 2-6 GHz region of the electromagnetic spectrum. Details of this upgraded spectrometer are reported.

Rotational Spectrum, Structure, and Interaction Energy of the Trifluoroethylene···Carbon Dioxide Complex.

Rotational spectra for four isotopologues of the 1:1 weakly bound complex between trifluoroethylene (HFC═CF) and carbon dioxide (CO) were recorded using 480 MHz bandwidth chirped-pulse and resonant cavity Fourier transform microwave spectroscopy between 5.0 and 18.5 GHz.

Effect of aromatic ring fluorination on CHπ interactions: microwave spectrum and structure of the 1,2-difluorobenzeneacetylene dimer.

Rotational spectra for the normal isotopic species and for six additional isotopologues of the 1,2-difluorobenzeneacetylene (C6H4F2HCCH) weakly bound dimer have been assigned in the 6-18 GHz region using chirped-pulse Fourier-transform microwave spectroscopy. This is the third complex in a series of fluorinated benzeneacetylene dimers. In 1,2-difluorobenzeneHCCH, the Hπ distance (2.

Rotational Spectrum and Structure of the 1,1-Difluoroethylene···Carbon Dioxide Complex.

Rotational spectra for five isotopologues of the 1:1 weak complex between 1,1-difluoroethylene (H2C═CF2) and carbon dioxide (CO2) have been measured using 480 MHz bandwidth chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy between 5.5 and 18.5 GHz.

Alkynes as CH/π Acceptors: Microwave Spectra and Structures of the CH2F2···Propyne and CH2ClF···Propyne Dimers.

Rotational spectra of weakly bound complexes of chlorofluoromethane (CH2ClF) and difluoromethane (CH2F2) with propyne (HCCCH3) have been measured using chirped-pulse and resonant-cavity Fourier-transform microwave spectroscopy, adding to a relatively small body of high resolution spectroscopic data on propyne complexes. Both dimers contain CH/π contacts, as well as secondary contacts between one or both halogen atoms and the methyl group of propyne. A detailed structural determination for CH2F2···propyne has been made by study of the normal, one deuterated and four (13)C substituted isotopologues, with the second lowest energy configuration predicted from ab initio calculations agreeing well with the observed structure.

Characterization of two isomers of the vinyl fluoride···carbon dioxide dimer by rotational spectroscopy.

Rotational spectra of two different structural forms of the 1:1 weak complex between vinyl fluoride (C2H3F) and carbon dioxide were measured using 480 MHz bandwidth chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy in the 5-17 GHz region. Both structures have the CO2 molecule situated in the plane of the vinyl fluoride, such that the CO2 is interacting either with a CHF side or with a HC═CF edge of the vinyl fluoride subunit. Both observed structures are close to those predicted by ab initio geometry optimizations (corrected for basis set superposition error) at the MP2/6-311++G(2d,2p) level.

A naturalistic comparison of the long-term metabolic adverse effects of clozapine versus other antipsychotics for patients with psychotic illnesses.

Objective: Clozapine, an evidence-based treatment of refractory schizophrenia, is associated with increased weight gain and metabolic dysregulation compared with most antipsychotics in short-term clinical trials. However, there are limited data describing comparative long-term metabolic risks. In this report, we examined whether short-term differences persist with long-term exposure to clozapine.

Benzene···acetylene: a structural investigation of the prototypical CH···π interaction.

The structure of a prototype CH···π system, benzene···acetylene, has been determined in the gas phase using Fourier-transform microwave spectroscopy. The spectrum is consistent with an effective C(6v) structure with an H···π distance of 2.4921(1) Å.

Rotational spectroscopic studies of C-H · · · F interactions in the vinyl fluoride · · · difluoromethane complex.

Rotational spectra of the normal isotopic species and three (13)C isotopologues of the 1:1 complex between vinyl fluoride (CH2 ═ CHF) and difluoromethane (CH2F2) have been measured using 480 MHz bandwidth chirped-pulse Fourier-transform microwave spectroscopy in the 6.5-20 GHz region. A structure for this dimer has been determined by fitting the moments of inertia of all isotopologues and confirmed by calculation of Kraitchman single isotopic substitution coordinates.

Effect of aromatic ring fluorination on CH···π interactions: rotational spectrum and structure of the fluorobenzene···acetylene weakly bound dimer.

The rotational spectra for the normal isotopic species and for six (13)C singly substituted isotopologues (in natural abundance) of the fluorobenzene···acetylene (C6H5F···HCCH) weakly bound dimer have been measured in the 6.5-18.5 GHz region using chirped-pulse Fourier-transform microwave spectroscopy.

Molecular structure of methyldifluoroisocyanato silane: a combined microwave spectral and theoretical study.

The structure of methyldifluoroisocyanato silane, MeF2SiNCO (2), has been studied by molecular rotational spectroscopy. The rotational spectrum has a complicated structure from (14)N nuclear quadrupole coupling and internal rotation of the methyl group. Cavity Fourier-transform microwave spectroscopy measurements were important for providing high spectral resolution to analyze the quadrupole and internal rotation fine structure.

Microwave, infrared and Raman spectra, r0 structural parameters, ab initio calculations and vibrational assignment of 1-fluoro-1-silacyclopentane.

The microwave spectrum (6500-18 ,500 MHz) of 1-fluoro-1-silacyclopentane, c-C(4)H(8)SiHF has been recorded and 87 transitions for the (28)Si, (29)Si, (30)Si, and (13)C isotopomers have been assigned for a single conformer. Infrared spectra (3050-350 cm(-1)) of the gas and solid and Raman spectrum (3100-40 cm(-1)) of the liquid have also been recorded. The vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twist form.

C-H···π interactions in the CHBrF2···HCCH weakly bound dimer.

The microwave spectra of four isotopologues of the CHBrF(2)···HCCH weakly bound dimer have been measured in the 6-18 GHz region using chirped-pulse and Balle-Flygare Fourier-transform microwave spectroscopy. Spectra of (13)CH(79)BrF(2) and (13)CH(81)BrF(2) monomers have also been measured, and spectroscopic constants are reported. Measurement of spectra for the (79)Br and (81)Br isotopologues of CHBrF(2) complexed with both (12)C(2)H(2) and (13)C(2)H(2) have allowed the determination of a structure with C(s) symmetry for this complex.

Observation of a double C-H···π interaction in the CH2ClF···HCCH weakly bound complex.

The structure of the CH(2)ClF···HCCH dimer has been determined using both chirped-pulse and resonant cavity Fourier-transform microwave spectroscopy. The complex has C(s) symmetry and contains both a double C-H···π interaction, in which one π-bond acts as acceptor to two hydrogen atoms from the CH(2)ClF donor, and a weak C-H···Cl interaction, with acetylene as the donor. Analysis of the rotational spectra of four isotopologues (CH(2)(35)ClF···H(12)C(12)CH, CH(2)(37)ClF···H(12)C(12)CH, CH(2)(35)ClF···H(13)C(13)CH, and CH(2)(37)ClF-H(13)C(13)CH) has led to a structure with C-H···π distances of 3.

Characterization of C-H...π interactions in the structure of the CHClF(2)-HCCH weakly bound complex.

The microwave spectra of four isotopologues of the CHClF(2)-HCCH dimer have been measured and used to determine the structure of the complex. An initial scan over the 7-18 GHz region using the chirped-pulse microwave spectrometer at the University of Virginia provided initial assignments of the (35)Cl and (37)Cl isotopologues, with two additional H(13)C(13)CH species assigned using the resonant cavity Balle-Flygare microwave spectrometer at Eastern Illinois University. For the most abundant isotopologue, the rotational constants and quadrupole coupling constants are: A = 3301.

Immersing practitioners in the recovery model: an educational program evaluation.

The ascendance of the recovery movement in mental health care has led to the development and implementation of educational curricula for mental health providers to assist in mental health care system transformation efforts. The Medical College of Georgia (MCG) partnered with the Georgia State Department of Human Resources (DHR) to develop, implement, and evaluate such an educational curriculum for providers within an academic medical institution. This effort, entitled Project GREAT, led to the creation of a curriculum based on the SAMHSA-defined (2006) critical components of recovery.

Microwave spectra and barrier to internal rotation in cyclopropylmethylsilane.

Rotational spectra for 3 silicon isotopologues (28Si, 29Si, 30Si) of cyclopropylmethylsilane (c-C3H5SiH2CH3) have been observed in natural abundance using Fourier-transform microwave spectroscopy, and the dipole moment of the most abundant (28Si) isotopologue has been determined using the Stark effect. The observed rotational constants (A = 8800.5997(9) MHz; B = 2238.

Rotational spectra and conformational analysis of diethylsilane and diethyldifluorosilane.

The rotational spectra belonging to the (28)Si isotopologue for three conformers of diethyldifluorosilane (Et(2)SiF(2)) and three conformers of diethylsilane (Et(2)SiH(2)) have been measured between 4 and 17 GHz by using pulsed-jet Fourier-transform microwave spectroscopy. Rotational spectra for the gauche-gauche, trans-trans, and trans-gauche conformers were identified for both molecules, while the significantly higher energy gauche-gauche' conformer was not observed. Ab initio calculations at the MP2(Full)/6-311+G(2d,2p) and MP2(Full)/6-311+G(2df,2pd) levels for the fluorine and the hydrogen analogues, respectively, provided rotational constants, dipole moment components, and the relative energies of the conformers to assist in the spectral assignment.

Dimers of fluorinated methanes with carbonyl sulfide: the rotational spectrum and structure of difluoromethane-OCS.

The pure rotational spectra of four isotopologues of the difluoromethane-carbonyl sulfide dimer have been measured in the 5-15 GHz region with use of pulsed-nozzle Fourier-transform microwave spectroscopy. The complex was determined to possess an ab plane of symmetry with a center of mass separation of 3.41(2) A and dipole moment components mu(a) = 1.

Microwave spectrum, dipole moment, and internal dynamics of the methyl fluoride-carbonyl sulfide weakly bound complex.

Rotational spectra for the normal and four isotopically substituted species of the 1:1 complex between methyl fluoride (H3CF) and carbonyl sulfide (OCS) have been measured using Fourier-transform microwave spectroscopy in the 5-16 GHz frequency region. The observed spectra fit well to a semirigid Watson Hamiltonian, and an analysis of the rotational constants has allowed a structure to be determined for this complex. The dipole moment vectors of the H3CF and OCS monomers are aligned approximately antiparallel with a C.

Oxygen-17 hyperfine structures in the pure rotational spectra of SrO, SnO, BaO, HfO and ThO.

Hyperfine structures arising from the couplings of the nuclear spin angular momentum of (17)O (I = 5/2) with the end over end rotation of several metal-containing diatomic monoxides have been observed using a Fourier transform microwave spectrometer. The molecules have been produced by reacting (17)O(2) with laser ablated metal atoms. The oxygen-17 nuclear quadrupole coupling constants have been determined for the title molecules and are interpreted in terms of a simple Townes-Dailey model.

Recovery and systems transformation for schizophrenia.

The Recovery Movement, initiated in the 1990s by mental health consumer groups and leaders, has emerged as a major force in the mental health field. This movement has been gaining strength and promises to impact mental health service delivery through innovations in care that other models of care have not offered. Recent efforts to conceptualize and study recovery empirically have bolstered the movement from a scientific standpoint.