Department of Chemistry

Physical and Theoretical Chemistry

Research ImageThe Department of Chemistry at the University of North Carolina at Chapel Hill, offers a wide range of research opportunities in theoretical and experimental physical chemistry. Our program has broadened from its traditional areas of excellence in molecular chemical physics to include research activities in biophysical and surface chemistry, and materials and environmental sciences. Experimental efforts within these areas utilize state-of-the-art instrumentation, such as high-resolution and ultra-fast laser systems, molecular beam techniques, mass spectrometry, ion-scattering, scanning probe microscopy, and magnetic resonance spectrometry.

Research in theoretical chemistry involves developing computational models of chromatin, the structure of complex fluids, and polymer dynamics. Students at UNC have access to high-performance computer workstations, as well as RENCI/UNC Research Computing, which is home to one of the best computing facilities in the world, including a 4160-processor Dell Linux cluster.


Recent Research Highlights

Melittin Reorientation

An important step in a phospholipid membrane pore formation by melittin antimicrobial peptide is a reorientation of the peptide from a surface into a transmembrane conformation. Experiments measure the fraction of peptides in the surface state and the transmembrane state, but no computational study exists that quantifies the free energy curve for the reorientation. In an article published in the Journal of Physical Chemistry B, researchers in the Berkowitz Group, in collaboration with the Max Planck Institute, perform umbrella sampling simulations to calculate the potential of mean force, PMF, for the reorientation of melittin from a surface-bound state to a transmembrane state and provide a molecular level insight in understanding the peptide-lipid properties that influence the existence of the free energy barrier.

Research Image

The PMFs were calculated for a peptide to lipid (P/L) ratio of 1/128 and 4/128. The group observed that the free energy barrier is reduced when the P/L ratio increases. In addition, they studied the cooperative effect; specifically investigating if the reorientation barrier is smaller for a second melittin, given that another neighboring melittin was already in the transmembrane orientation. The group observed that indeed the barrier of the PMF curve is reduced in this case, thus confirming the presence of a cooperative effect.


Ultrafast Dynamics in DNA Components

Researchers in the Moran Group, as published in the Journal of Physical Chemistry A, are using femtosecond laser spectroscopies to examine a thymine family of systems chosen to expose the interplay between excited state deactivation and two distinct vibrational energy transfer (VET) pathways. One from the base to the deoxyribose ring, the second between neighboring units in a dinucleotide. They report that relaxation in the ground electronic state accelerates markedly as the molecular sizes increase from the nucleobase to the dinucleotide.

Research Image

Overall, the researchers conclude that the transfer of vibrational quanta from thymine to the deoxyribose ring couples significantly to the internal conversion rate, whereas the neighboring unit in the dinucleotide serves as a secondary heat bath. In natural DNA, it follows that (local) thermal fluctuations in the geometries of subunits involving the base and deoxyribose ring are most important to this subpicosecond relaxation process.


Representative Publications

Modeling Time-Coincident Ultrafast Electron Transfer and Solvation Processes at Molecule-Semiconductor Interfaces. Lesheng Li, Paul G. Giokas, Yosuke Kanai, and Andrew M. Moran. J. Chem. Phys. 140, 234109 (2014).

Imaging Charge Separation and Carrier Recombination in Nanowire p-i-n Junctions Using Ultrafast Microscopy. Michelle M Gabriel , Erik Grumstrup , Justin R. Kirschbrown , Christopher W. Pinion , Joseph D Christesen , David F. Zigler , Emma M Cating , James F. Cahoon , and John Michael Papanikolas. Nano Lett., Just Accepted Manuscript, DOI: 10.1021/nl5012118, Publication Date (Web): May 27, 2014.

Ultrafast Carrier Dynamics of Silicon Nanowire Ensembles: The Impact of Geometrical Heterogeneity on Charge Carrier Lifetime. Erik M. Grumstrup , Emma M. Cating , Michelle M. Gabriel , Christopher W. Pinion , Joseph D. Christesen , Justin R. Kirschbrown , Ernest L. Vallorz III, James F. Cahoon, and John M. Papanikolas. J. Phys. Chem. C, 2014, 118 (16), pp 8626–8633.

Ultrafast Carrier Dynamics in Individual Silicon Nanowires: Characterization of Diameter-Dependent Carrier Lifetime and Surface Recombination with Pump-Probe Microscopy. Erik M. Grumstrup , Michelle M. Gabriel , Emma M. Cating , Christopher W. Pinion , Joseph D. Christesen , Justin R. Kirschbrown , Ernest L. Vallorz III, James F. Cahoon, and John M. Papanikolas. J. Phys. Chem. C, 2014, 118 (16), pp 8634–8640.

Free Energy Barrier for Melittin Reorientation from a Membrane-Bound State to a Transmembrane State. Sheeba J. Irudayam, Tobias Pobandt, and Max L. Berkowitz. J. Phys. Chem. B, 2013, 117 (43), pp 13457–13463.

Interplay between Vibrational Energy Transfer and Excited State Deactivation in DNA Components. Brantley A. West, Jordan M. Womick, and Andrew M. Moran. J. Phys. Chem. A, 2013, 117 (29), pp 5865–5874.

Uncovering Molecular Relaxation Processes with Nonlinear Spectroscopies in the Deep UV. Brantley A. West, Brian P. Molesky, Paul G. Giokas, Andrew M. Moran. Chemical Physics, Volume 423, 23 September 2013, Pages 92-104.

Gas Phase Acidity Measurement of Local Acidic Groups in Multifunctional Species: Controlling the Binding Sites in Hydroxycinnamic Acids. Andres Guerrero, Tomas Baer, Antonio Chana, Javier González, and Juan Z. Dávalos. J. Am. Chem. Soc., 2013, 135 (26), pp 9681–9690.

Melittin Creates Transient Pores in a Lipid Bilayer: Results from Computer Simulations. Kolattukudy P. Santo , Sheeba J. Irudayam , and Max L. Berkowitz. J. Phys. Chem. B, 2013, 117 (17), pp 5031–5042.

Pump–Probe Microscopy: Spatially Resolved Carrier Dynamics in ZnO Rods and the Influence of Optical Cavity Resonator Modes. Brian P. Mehl, Justin R. Kirschbrown, Michelle M. Gabriel, Ralph L. House, and John M. Papanikolas. J. Phys. Chem. B, 2013, 117 (16), pp 4390–4398.