Scholars@Duke
Richard MacPhail

Richard MacPhail

Associate Professor Emeritus of Chemistry
Chemistry
richard.macphail@duke.edu
Box 90346, Durham, NC 27708-0346
French Family Science Center, Room 1216, Durham, NC 27708
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Selected Publications

Developing metacognitive and problem-solving skills through problem manipulation

Journal Article Journal of Chemical Education · 2011 Featured Publication In a collaborative effort between the our universitys department of chemistry and the academic resource center, we designed a model for general chemistry recitation based on a problem manipulation method in which students actively assess the skills and kno ... Full text Cite

Solvent-solute interactions and the Raman CH stretching spectrum of cyclohexane-d11. II. Density dependence in supercritical carbon dioxide

Journal Article Journal of Chemical Physics · January 15, 1999 We have measured the isotropic Raman CH stretching spectrum of cyclohexane-d11 in supercritical CO2 at 49.7 °C and in liquid CO2 at room temperature over a range of densities from 0.2ρc to 2ρc, where the critical number density ρc for CO2 is 6.4 nm-3. The ... Full text Cite

Physical aging in supercooled glycerol: Evidence for heterogeneous dynamics?

Journal Article Journal of Physical Chemistry B · October 23, 1997 Several recent experiments on glycerol and other supercooled liquids have suggested that dynamically heterogeneous domains in the liquid are responsible for the nonexponential structural relaxation dynamics observed near the glass transition. In addition, ... Full text Cite

The fully integrated, computer based Physical Chemistry Laboratory

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 7, 1997 Link to item Cite

Ultraslow nonequilibrium dynamics in supercooled glycerol by stimulated Brillouin gain spectroscopy

Journal Article Journal of Chemical Physics · February 22, 1997 We have used high resolution stimulated Brillouin gain spectroscopy to monitor the nonequilibrium relaxation dynamics of supercooled glycerol near its glass transition temperature. After a temperature quench from 192.4 to 179.8 K, the Brillouin frequency s ... Full text Cite

Complex dynamics and the stimulated gain spectrum of pentylcyanobiphenyl in the isotropic phase

Journal Article Chemical Physics Letters · July 14, 1995 We have measured high resolution polarized and depolarized stimulated gain spectra of the liquid crystal pentylcyanobiphenyl (5CB) in its isotropic phase between 36.2 and 122°C. Spectral features associated with slow collective reorientation, acoustic wave ... Full text Cite

Solvent-solute interactions and the Raman CH stretching spectrum of cyclohexane-d11: I. Solvent-dependence

Journal Article The Journal of Chemical Physics · January 1, 1995 We examine the gas-to-liquid frequency shifts and isotropic Raman linewidths for the axial and equatorial CH stretching vibrations of cyclohexane-d11 in 13 different solvents. The "perturbed hard-fluid model" of Ben-Amotz and Herschbach provides a consiste ... Full text Cite

High resolution stimulated Brillouin gain spectrometer

Journal Article Review of Scientific Instruments · December 1, 1994 We describe a stimulated Brillouin gain (SBG) spectrometer based on low power continuous-wave frequency-stabilized lasers. The high resolution and broad tuning range of this spectrometer are demonstrated through a SBG spectrum of glycerol in the glassy sta ... Full text Cite

PSEUDOROTATION DYNAMICS OF CYCLOPENTANE-D(9) AS A FUNCTION OF SOLVENT DENSITY

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · March 13, 1994 Link to item Cite

Dynamics in supercooled glycerol by high resolution stimulated Brillouin gain spectroscopy

Journal Article The Journal of Chemical Physics · January 1, 1994 We have used high resolution stimulated Brillouin gain spectroscopy to probe the dynamics of glycerol over the temperature ranges 146 to 305 K and 401 to 534 K, which include both the supercooled liquid and glass regimes. The high resolution and large spec ... Full text Cite

A Raman study of cyclopentane-d9 pseudorotation dynamics as a function of pressuer

Journal Article Chemical Physics Letters · September 3, 1993 We have measured isotropic Raman CH stretching spectra of a cyclopentane-d9/CO2 gaseous mixture at various pressures up to 48.2 bar (700 psi). With increasing pressure the spectra broaden and exhibit partial motional narrowing due, in part, to changes in t ... Full text Cite

Variable temperature infrared spectroscopy of cytosine-guanine base pairs: tautomerism versus polarization.

Journal Article Journal of biomolecular structure & dynamics · April 1992 This report describes an infrared (IR) spectroscopic study of a model cytosine-guanine base pair. This base pair is part of a self-consistent experimental system based on lipophilic ribose derivatives of cytidine (C), guanosine (G) and O6-methylguanosine ( ... Full text Cite

CW-stimuIated Brillouin gain spectroscopy of liquids, supercooled liquids, and glasses

Conference Optics InfoBase Conference Papers · January 1, 1992 Cite

Pseudorotation and the raman CH stretching spectrum of gaseous cyclopentane-d9: Local modes in a floppy molecule

Journal Article The Journal of Physical Chemistry · January 1, 1992 The deuterium-isolated CH stretching band in the isotropic Raman spectrum of gaseous cyclopentane-d9 shows structure associated with the pseudorotation dynamics of the ring. This structure can be reproduced by a theoretical calculation that uses the adiaba ... Full text Cite

High-resolution stimulated Brillouin gain spectroscopy of liquid carbon disulfide: Dependence of the linewidths and peak gain on scattering angle

Journal Article The Journal of Chemical Physics · January 1, 1992 We have used narrow linewidth continuous-wave lasers to obtain high-resolution stimulated Brillouin gain (SBG) spectra of liquid carbon disulfide at various scattering angles. For back-scattering angles, the linewidths of the SBG peaks reflect the natural ... Full text Cite

High-resolution stimulated Brillouin gain spectroscopy of liquid benzene shows no evidence of a "structural transition"

Journal Article Journal of Physical Chemistry · January 1, 1992 We have used high-resolution stimulated Brillouin gain spectroscopy to search for evidence of a "structural transition" within the liquid phase of benzene. On the basis of previous measurements of depolarized light scattering intensities and Brillouin line ... Full text Cite

Rotational-translational coupling and asymmetric line shapes in the high resolution stimulated Brillouin gain spectra of liquid carbon disulfide

Journal Article The Journal of Chemical Physics · January 1, 1992 We have measured high resolution stimulated Brillouin gain spectra of liquid carbon disulfide at a number of temperatures between 158 and 301 K. As the temperature decreases the shape of the Brillouin peak becomes increasingly asymmetric, with the intensit ... Full text Cite

cw stimulated Brillouin gain spectroscopy of liquids

Journal Article Chemical Physics Letters · August 2, 1991 We demonstrate the use of cw stimulated Brillouin gain (SBG) spectroscopy to measure high resolution Brillouin spectra of liquids. Results are reported for thirteen liquids at room temperature, all obtained in a polarized (VV) configuration with a scatteri ... Full text Cite

Frequency-dependent solvent friction and torsional damping in liquid 1,2-difluoroethane

Journal Article Chemical Physics · April 15, 1991 We have used Raman spectroscopy to study the torsional dynamics, rotational dynamics, and conformational solvation energy of liquid 1,2-difluoroethane. From the Raman intensities, we obtain ΔH(g-t) = -2.4±0.1 kcal/mol, indicating strong dipolar solvation o ... Full text Cite

Developing metacognitive and problem-solving skills through problem manipulation

Journal Article Journal of Chemical Education · 2011 Featured Publication In a collaborative effort between the our universitys department of chemistry and the academic resource center, we designed a model for general chemistry recitation based on a problem manipulation method in which students actively assess the skills and kno ... Full text Cite

Solvent-solute interactions and the Raman CH stretching spectrum of cyclohexane-d11. II. Density dependence in supercritical carbon dioxide

Journal Article Journal of Chemical Physics · January 15, 1999 We have measured the isotropic Raman CH stretching spectrum of cyclohexane-d11 in supercritical CO2 at 49.7 °C and in liquid CO2 at room temperature over a range of densities from 0.2ρc to 2ρc, where the critical number density ρc for CO2 is 6.4 nm-3. The ... Full text Cite

Physical aging in supercooled glycerol: Evidence for heterogeneous dynamics?

Journal Article Journal of Physical Chemistry B · October 23, 1997 Several recent experiments on glycerol and other supercooled liquids have suggested that dynamically heterogeneous domains in the liquid are responsible for the nonexponential structural relaxation dynamics observed near the glass transition. In addition, ... Full text Cite

The fully integrated, computer based Physical Chemistry Laboratory

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · September 7, 1997 Link to item Cite

Ultraslow nonequilibrium dynamics in supercooled glycerol by stimulated Brillouin gain spectroscopy

Journal Article Journal of Chemical Physics · February 22, 1997 We have used high resolution stimulated Brillouin gain spectroscopy to monitor the nonequilibrium relaxation dynamics of supercooled glycerol near its glass transition temperature. After a temperature quench from 192.4 to 179.8 K, the Brillouin frequency s ... Full text Cite

Complex dynamics and the stimulated gain spectrum of pentylcyanobiphenyl in the isotropic phase

Journal Article Chemical Physics Letters · July 14, 1995 We have measured high resolution polarized and depolarized stimulated gain spectra of the liquid crystal pentylcyanobiphenyl (5CB) in its isotropic phase between 36.2 and 122°C. Spectral features associated with slow collective reorientation, acoustic wave ... Full text Cite

Solvent-solute interactions and the Raman CH stretching spectrum of cyclohexane-d11: I. Solvent-dependence

Journal Article The Journal of Chemical Physics · January 1, 1995 We examine the gas-to-liquid frequency shifts and isotropic Raman linewidths for the axial and equatorial CH stretching vibrations of cyclohexane-d11 in 13 different solvents. The "perturbed hard-fluid model" of Ben-Amotz and Herschbach provides a consiste ... Full text Cite

High resolution stimulated Brillouin gain spectrometer

Journal Article Review of Scientific Instruments · December 1, 1994 We describe a stimulated Brillouin gain (SBG) spectrometer based on low power continuous-wave frequency-stabilized lasers. The high resolution and broad tuning range of this spectrometer are demonstrated through a SBG spectrum of glycerol in the glassy sta ... Full text Cite

PSEUDOROTATION DYNAMICS OF CYCLOPENTANE-D(9) AS A FUNCTION OF SOLVENT DENSITY

Conference ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY · March 13, 1994 Link to item Cite

Dynamics in supercooled glycerol by high resolution stimulated Brillouin gain spectroscopy

Journal Article The Journal of Chemical Physics · January 1, 1994 We have used high resolution stimulated Brillouin gain spectroscopy to probe the dynamics of glycerol over the temperature ranges 146 to 305 K and 401 to 534 K, which include both the supercooled liquid and glass regimes. The high resolution and large spec ... Full text Cite

A Raman study of cyclopentane-d9 pseudorotation dynamics as a function of pressuer

Journal Article Chemical Physics Letters · September 3, 1993 We have measured isotropic Raman CH stretching spectra of a cyclopentane-d9/CO2 gaseous mixture at various pressures up to 48.2 bar (700 psi). With increasing pressure the spectra broaden and exhibit partial motional narrowing due, in part, to changes in t ... Full text Cite

Variable temperature infrared spectroscopy of cytosine-guanine base pairs: tautomerism versus polarization.

Journal Article Journal of biomolecular structure & dynamics · April 1992 This report describes an infrared (IR) spectroscopic study of a model cytosine-guanine base pair. This base pair is part of a self-consistent experimental system based on lipophilic ribose derivatives of cytidine (C), guanosine (G) and O6-methylguanosine ( ... Full text Cite

CW-stimuIated Brillouin gain spectroscopy of liquids, supercooled liquids, and glasses

Conference Optics InfoBase Conference Papers · January 1, 1992 Cite

Pseudorotation and the raman CH stretching spectrum of gaseous cyclopentane-d9: Local modes in a floppy molecule

Journal Article The Journal of Physical Chemistry · January 1, 1992 The deuterium-isolated CH stretching band in the isotropic Raman spectrum of gaseous cyclopentane-d9 shows structure associated with the pseudorotation dynamics of the ring. This structure can be reproduced by a theoretical calculation that uses the adiaba ... Full text Cite

High-resolution stimulated Brillouin gain spectroscopy of liquid carbon disulfide: Dependence of the linewidths and peak gain on scattering angle

Journal Article The Journal of Chemical Physics · January 1, 1992 We have used narrow linewidth continuous-wave lasers to obtain high-resolution stimulated Brillouin gain (SBG) spectra of liquid carbon disulfide at various scattering angles. For back-scattering angles, the linewidths of the SBG peaks reflect the natural ... Full text Cite

High-resolution stimulated Brillouin gain spectroscopy of liquid benzene shows no evidence of a "structural transition"

Journal Article Journal of Physical Chemistry · January 1, 1992 We have used high-resolution stimulated Brillouin gain spectroscopy to search for evidence of a "structural transition" within the liquid phase of benzene. On the basis of previous measurements of depolarized light scattering intensities and Brillouin line ... Full text Cite

Rotational-translational coupling and asymmetric line shapes in the high resolution stimulated Brillouin gain spectra of liquid carbon disulfide

Journal Article The Journal of Chemical Physics · January 1, 1992 We have measured high resolution stimulated Brillouin gain spectra of liquid carbon disulfide at a number of temperatures between 158 and 301 K. As the temperature decreases the shape of the Brillouin peak becomes increasingly asymmetric, with the intensit ... Full text Cite

cw stimulated Brillouin gain spectroscopy of liquids

Journal Article Chemical Physics Letters · August 2, 1991 We demonstrate the use of cw stimulated Brillouin gain (SBG) spectroscopy to measure high resolution Brillouin spectra of liquids. Results are reported for thirteen liquids at room temperature, all obtained in a polarized (VV) configuration with a scatteri ... Full text Cite

Frequency-dependent solvent friction and torsional damping in liquid 1,2-difluoroethane

Journal Article Chemical Physics · April 15, 1991 We have used Raman spectroscopy to study the torsional dynamics, rotational dynamics, and conformational solvation energy of liquid 1,2-difluoroethane. From the Raman intensities, we obtain ΔH(g-t) = -2.4±0.1 kcal/mol, indicating strong dipolar solvation o ... Full text Cite

A Raman study of solvent effects on n-butane: Torsional dynamics, rotational dynamics, and conformational equilibrium

Journal Article Journal of Physical Chemistry · January 1, 1991 We have measured Raman spectra of n-butane dissolved in four solvents, carbon disulfide, benzene, methanol, and cyclopentene. From the band intensities of the in-phase skeletal bending modes of the gauche (325 cm-1) and trans (430 cm-1) conformers, we have ... Full text Cite

Raman spectroscopic study of reaction dynamics

Journal Article Journal of Physics: Condensed Matter · December 1, 1990 The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-but ... Full text Cite

Pseudorotation dynamics in liquid cyclopentane by Raman spectroscopy

Journal Article Chemical Physics Letters · September 15, 1989 We have measured isotropic Raman spectra of cyclopentane-d9 in the CH stretching region from 180 to 300 K. The spectra show what is apparently a partial motional averaging of the CH stretching bands by pseudorotation, a barrierless conformational rearrange ... Full text Cite

Relaxation in supercooled liquids: Similarities between projected and unprojected correlation functions

Journal Article The Journal of Chemical Physics · January 1, 1989 We have examined and interrelated a number of different relaxation processes in supercooled liquids by use of molecular correlation functions, some of which are newly developed and have projected dynamics. Experimentally it is found that in supercooled liq ... Full text Cite

Relaxation in supercooled liquids: A generalized hydrodynamic description

Journal Article The Journal of Chemical Physics · January 1, 1989 We focus on the frequency dependence of the viscosity η(ω), or more specifically, of the retardational compliance Jr(ω), for supercooled liquids. We pursue a phenomenological approach which is related to extended hydrodynamics and is of a form compatible w ... Full text Cite

Torsional damping and solvent friction in liquid n-butane: Experimental estimates from Raman spectroscopy

Journal Article The Journal of Chemical Physics · January 1, 1989 The isotropic Raman linewidths of the in-phase CCC bending modes of liquid n-butane are analyzed in terms of dephasing by torsional oscillations. A simple, effective Hamiltonian is developed to calculate the coupling between this bending mode and the torsi ... Full text Cite

Effects of Torsion on the 13C Chemical Shift in Ethane

Journal Article Chem. Phys. Lett. · 1988 Cite

Nonlinear ultrasonically induced birefringence in gold sols: Frequency-dependent diffusion

Journal Article Physical Review A · January 1, 1986 Ultrasonically induced birefringence has been used to study coupled translational and rotational motions of large (100-nm) nonspherical colloidal gold particles in fluids. The effect is nonlinear in that the induced birefringence is quadratic in the ultras ... Full text Cite

Viscoelasticity the high-frequency viscosity factorf

Journal Article Molecular Physics · April 10, 1985 We study the behaviour in viscoelastic fluids of the high-frequency viscosity factor C(n(ωm)). This factor depends upon the number n(ωm) of exponential decay terms needed to describe the observed relaxation behaviour in a frequency range 0 to com. Quite ge ... Full text Cite

Can the Bloch equations describe the vibrational spectra of a reacting molecule?

Journal Article The Journal of Chemical Physics · January 1, 1985 The vibrational spectra of molecules that are rapidly interconverted among distinct species by very fast motions, for example, during ordinary chemical reactions or during the rotation of a molecule between different sites in a solid, are considered. The q ... Full text Cite

Visoelasticity. The High-Frequency Viscosity Factor

Journal Article Molec. Phys. · 1985 Cite

C-H stretching modes and the structure of n-alkyl chains. 2. Long, all-trans chains

Journal Article Journal of Physical Chemistry · January 1, 1984 The C-H and C-D stretching bands in the infrared spectra of some crystalline n-alkanes at low temperature (<10 K) have been measured and analyzed. Most of the n-alkanes studied contain 16-22 carbons, and all are in the all-trans conformation. Assignments a ... Full text Cite

Generalized hydrodynamic theory of viscoelasticity

Journal Article The Journal of Chemical Physics · January 1, 1983 A generalized hydrodynamic treatment of the dynamic behavior of transverse phenomena in a fluid is presented. An attempt is made to describe such phenomena (VH depolarized light scattering, flow birefringence, transverse sound or shear waves and viscous fl ... Full text Cite

Local mode spectra of inequivalent C-H oscillators in cycloalkanes and cycloalkenes

Journal Article Journal of Physical Chemistry · January 1, 1982 Local mode spectra of cycloalkanes and cycloalkenes are observed by using both gas-phase high overtone and isotopically isolated fundamental spectroscopy. The shapes of the bands reflect the changes in the C-H bonds during the conformational motion. Absorp ... Full text Cite

The motional collapse of the methyl C-H stretching vibration bands

Journal Article The Journal of Chemical Physics · January 1, 1982 The asymmetric CH stretching bands of the methyl groups of a number of alkane systems have been examined as a function of temperature. At low temperatures, two bands are seen for a CH3 group. These bands collapse into one as the temperature is raised. Exam ... Full text Cite

A Local Mode Description of the CH-Stretching Overtone Spectra of the Cycloalkanes and Cycloalkenes

Journal Article Journal of the American Chemical Society · January 1, 1980 The overtone spectra of the cycloalkanes, cyclopentane to cyclooctane, and three cycloalkenes (cyclopentene, cyclohexene, and cycloheptene) are measured in the liquid phase up to ∆vCH = 7 for the cycloalkanes and up to ∆vCH = 6 for the cycloalkenes. The pr ... Full text Cite

Motional Collapse of Methyl Group Vibrational Bands

Journal Article Journal of the American Chemical Society · January 1, 1980 Full text Cite

Vibrational spectra for trans-dimethyldiazene-1,1,1-d3 (azomethane). Potential functions for trans-dimethyldiazene and trans-methyldiazene

Journal Article The Journal of Chemical Physics · January 1, 1978 Gas-phase and matrix infrared spectra and gas-, liquid-, and solid-phase Raman spectra of trans-dimethyldiazene-1,1,1-d3 (CH3N = NCD3) have been recorded. A complete vibrational assignment has been secured for this molecule based on direct observation of 2 ... Full text Cite

Vibrational assignments and a potential function for 3,3-difluorocyclopropene-d0, -d1, and -d2

Journal Article Journal of Physical Chemistry · 1978 Complete assignments of the vibrational fundamentals of 3,3-difluorocyclopropene and its d1 and d2 isotopic modifications are derived from infrared and Raman spectra. The 15 fundamentals for the undeuterated molecule are as follows, in cm-1: (a1) 3150, 159 ... Cite

Cis-Dimethyldiazene

Journal Article Journal of the American Chemical Society · January 1, 1977 Full text Cite