6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

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Quantum mechanical continuum solvation models.

Ranging from the physics of elementary particles to the structure of viruses, the subject matter of this book stresses the importance of optical activity and chirality in modern science and will be of interest to a wide range of scientists. Using classical and quantum methods with a strong emphasis on symmetry principles, the volume develops the theory of varied optical activity and related phenomena from the perspective of molecular scattering of polarized light. First Edition Hb (1983): 0-521-24602-4

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Molecular Light Scattering and Optical Activity

Aqueous surfaces and interfaces are important in many physical, chemical, and biological processes in our world. The adsorption, dissolution, and reaction of atmospheric gases at the surfaces of atmospheric aerosols and oceanic waters play a key role in the composition of our atmosphere and the sustainability of plant and animal species in land waters. The transport and exchange of ions and solutes across the interface between an aqueous phase and hydrophobic biomolecular assemblies underlies some of the most important processes in living plants and animals. Membrane formation, protein folding, and micelle formation all involve, and are often controlled by, bonding interactions with water molecules at their surfaces. The unique physical, chemical, and biological properties of aqueous surfaces arise from the strong hydrogen bonding that occurs between water molecules and the asymmetry in this otherwise tetrahedral bonding coordination that results from the termination of the bulk water phase. Although there has been increased experimental and theoretical effort in recent years focused on developing a molecular picture of the structure and bonding of water layers to other solid, liquid, and gaseous media, consensus on the details of interfacial bonding has been slow or nonexistent in many areas. The adsorption of ions, surfactants, and solute molecules at these interfaces adds a level of complexity to the Geraldine Richmond holds the Richard M. and Patricia H. Noyes Professor of Chemistry position at the University of Oregon. She received her Ph.D. degree under the mentorship of George Pimentel at the University of California, Berkeley, in 1980. From 1980 to 1985 she was on the faculty at Bryn Mawr College and moved to the University of Oregon in 1985 as an associate professor. Richmond is recognized for her fundamental studies of the structure, dynamics, and bonding characteristics of surfaces and interfaces. Her research group uses a combination of linear and nonlinear optical methods, thermodynamic measurements, and theory to characterize interactions at aqueous surfaces, metal and semiconductor surfaces in contact with liquids and adsorbates, and liquid/liquid interfaces. Richmond has received several recent honors for these studies including the 2002 ACS Spectrochemical Analysis Award, the 2001 Oregon Scientist of the Year, and the 1996 Olin-Garvan Medal of the ACS and has been a Fellow of the American Physical Society since 1993. 2693 Chem. Rev. 2002, 102, 2693−2724

Molecular bonding and interactions at aqueous surfaces as probed by vibrational sum frequency spectroscopy.

X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption experiments on water are often interpreted in terms of hydrogen bonding. To this end a number of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liquid water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an estimate of the number of hydrogen bonds per molecule in liquid simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond number fluctuations, finding an approximate long-time decay constant for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.

Hydrogen bonding definitions and dynamics in liquid water.

Low frequency Δν=0–350 cm−1, Raman intensity data were obtained from liquid water between 3.5 and 89.3 °C using holographic grating double and triple monochromators. The spectra were Bose–Einstein (BE) corrected, I/(1+n), and the total integrated (absolute) contour intensities were treated by an elaboration of the Young–Westerdahl (YW) thermodynamic method, assuming conservation of hydrogen‐bonded (HB) and nonhydrogen‐bonded (NHB=bent and/or stretched, O–H O) nearest‐neighbor O–O pairs. A ΔH°1 value of 2.6±0.1 kcal/mol O–H ⋅⋅⋅ O or 5.2±0.2 kcal/mol H2O (11 kJ/mol O–H ⋅⋅⋅ O, or 22 kJ/mol H2O) resulted for the HB→NHB process. This intermolecular value agrees quantitatively with Raman and infrared ΔH° values from the one‐ and two‐phonon OH‐stretching regions, and from molecular dynamics, depolarized light scattering, neutron scattering, and ultrasonic absorption, thus indicating a common process. A population involving partial covalency of, i.e., charge transfer into, the H ⋅⋅⋅ O units of linear and/or weak...

Temperature dependence of the low‐ and high‐frequency Raman scattering from liquid water

Raman spectra and structure of water from -10 to 90.deg.

Raman circular intensity differential spectroscopy. Spectra of (-)-.alpha.-pinene and (+)-.alpha.-phenylethylamine

Raman spectra and structure of water in dimethyl sulfoxide

Fe(III), Cu(II), Co(III), and Mn(III) complexes of ovo- and human serum transferrins show resonance enhanced Raman bands near 1600, 1500, 1270, and 1170 cm-1 upon excitation with laser frequencies which fall within the visible absorption bands of those metalloproteins. Comparison of the visible absorption and resonance Raman spectra of the Cu(II)-transferrin complexes with those for the Cu(II) model compound, bis(2,4,6-trichlorophenolato)diimidazolecopper(II) monohydrate, indicates that the resonance Raman bands are due to enhancement of phenolic vibrational modes. For the model (Cu(II) compound, a normal coordinate analysis was used to aid our assignment of the observed resonance bands at 1562, 1463, 1311, and 1122 cm-1 to A1 vibrational modes of the 2,4,6-trichlorophenolato moiety. These assignments are consistent with those made for Cu(II)-transferrins. The latter assignments were based upon calculated A1 frequencies for p-methylphenol (Cummings, D.L., and Wood, J.L. (1974), J. Mol. Struct. 20, 1). The wavelength shifts in the resonance bands for the model compound from those for Cu(II)-transferrins are due to the influence of the chloro substituents on the planar vibrations of phenol. These results clearly identify tyrosine as a ligand in copper binding to transferrins.

Resonance Raman spectra of iron(III)-, copper(II)-, cobalt(III)-, and manganese(III)-transferrins and of bis(2,4,6-trichlorophenolato)diimidazolecopper(II) monohydrate, a possible model for copper(II) binding to transferrins.

Raman spectroscopy was used to study the effects of dehydratation on vibrational spectra of lipid and water in multilamellar dispersions of DMPC over a relative humidity (RH) of 99% RH to 0% RH. The Raman spectra indicated that at 30 and 40°C, removal of water induced at least two phase changes in the lipid.

Saima Kint

Papers

Raman spectra and structure of water from -10 to 90.deg.

Raman circular intensity differential spectroscopy. Spectra of (-)-.alpha.-pinene and (+)-.alpha.-phenylethylamine

Raman spectra and structure of water in dimethyl sulfoxide

Resonance Raman spectra of iron(III)-, copper(II)-, cobalt(III)-, and manganese(III)-transferrins and of bis(2,4,6-trichlorophenolato)diimidazolecopper(II) monohydrate, a possible model for copper(II) binding to transferrins.

Raman spectra of hydrated phospholipid bilayers. 2. Water and head-group interactions