Alexander V. Benderskii Title Assistant Professor Division Physical Education M.S. Moscow Institute of Physics and Technology (Russia), 1992 Ph.D. University of Utah, 1996 Postdoc, University of California, Irvine, 1996-99, Columbia University, 1999-2002 Office Chem 73 Phone (313)577-8658 E-Mail Group http://chem.wayne.edu/benderskii-group

Our research focuses on molecular structure and dynamics of surfaces and interfaces. Two complementary aspects of our research program (1) development of new and more powerful surface spectroscopy techniques with better sensitivity and detection limits, ultrafast time resolution, and improved molecular-level information content; (2) application of these techniques for fundamental and applied investigations of molecular organization and dynamics in these interesting and complex environments.

Currently, we are focusing on vibrational spectroscopy (mid-IR spectral range) because it provides a lot of information on the molecular structure and organization at surfaces and interfaces. To achieve surface selectivity, we utilize even-order nonlinear optical processes, such as Sum Frequency Generation (SFG) and Second Harmonic Generation (SHG), which are symmetry-forbidden in isotropic bulk media in the electric dipole approximation.

In addition to the standard frequency-domain spectroscopic measurements that characterize ensemble averaged structures, we are working on an array of ultrafast (femtosecond) time-domain techniques, such as SFG-FID (Free Induction Decay) for complementary studies of the molecular dynamics in real time. Our recent developments include a mixed Spectrally- and Time-Resolved SFG (STiR-SFG), a novel technique capable of measuring spectral evolution of vibrational coherences at surfaces, and heterodyne-detected SFG (HD-SFG) capable of ultrasensitive detection on a few percent of a monolayer level while simultaneously providing phase information on the molecular vibrations.

We are interested in systems important in life sciences, nano- and bio-technology, and material science. Current projects fall into three categories:

• Structure and dynamics of the hydrogen bonding network at aqueous interfaces, with the long-range goal of better understanding biomembrane surfaces. H-bonding underlies most of the important and unique properties of 'biological water', a thin layer adjacent to biointerfaces. Using ultrafast spectroscopy, we are systematically investigating how the dynamic aqueous H-bond network are affected by the chemical functionalities and electrostatics of interfaces.

• Molecular organization of monolayer and surface materials. Molecularly ordered surfaces and thin films are emerging as the base materials for nanoscale devices, molecular electronics, and biotechnologies. The 'tailored' surface materials under investigation include: Langmuir-Blodgett monolayers, Self-Assembled Monolayers, polymer surfaces, and bio-functionalized surfaces used, e.g., for cell adhesion. We study details of molecular orientation, conformation, packing, dynamics and relaxation, and surface functionalization chemistry at these surfaces.

• Surfaces and interfaces of nanostructures. A common motif in many emerging nanotechnology applications involves nanostructures covered with chemi- or physisorbed organic molecules which perform the desired physical, chemical, or biological function. We apply nonlinear spectroscopy to study organization, conformation, dynamics, and reactivity of molecules on surfaces of metal and semiconductor nanostructures, e.g. nanoparticles of different size and shape, and nanoparticle aggregates. In particular, we focus on the new effects arising when the characteristic size of the nanostructure approaches the molecular scale.

Stiopkin, I. V., Jayathilake, H. D.; Bordenyuk, A. N.; Benderskii, A.V. "Heterodyne-detected Vibrational Sum Frequency Generation Spectroscopy", J. Am. Chem. Soc. 130, 2271 -2275 (2008).

Bordenyuk, A. N.; Weeraman, C.; Yatawara, A. K.; Jayathilake, H. D.; Stiopkin, I. V.; Liu, Y.; Benderskii, A. V. "Vibrational Sum Frequency Generation Spectroscopy of Dodecanethiol on Metal Nanoparticles" J. Phys. Chem. C 111, 8925-8933 (2007)

Weeraman, C.; Yatawara, A. K.; Bordenyuk, A.N.; Benderskii, A.V. "Effect of Nanoscale Geometry on Molecular Conformation: Vibrational Sum-Frequency Generation of Alkanethiols on Gold Nanoparticles" J. Am. Chem. Soc. 128, 14244 - 14245 (2006).

Jayathilake, H.D.; Bordenyuk, A.N.; Weeraman, C.; Zhu, M.; Rosenblatt, C.; Benderskii, A.V. "Rubbing-induced anisotropy of alkyl side chains orientation at polyimide surfaces", J. Chem. Phys. 125, 064706 (2006).

Bordenyuk, A.N.; Jayathilake, H.; Benderskii, A. V. "Coherent Vibrational Quantum Beats as a Probe of Langmuir-Blodgett Monolayers", J. Phys. Chem. B 109, 15941 (2005). Cover illustration.

Bordenyuk, A.N.; Benderskii, A. V. "Spectrally- and Time-Resolved Vibrational Surface Spectroscopy: Ultrafast Hydrogen Bonding Dynamics at D2O/CaF2 Interface" J. Chem. Phys. 122, 134713 (2005). Selected for publication in: Virtual Journal of Ultrafast Science (May 2005 issue) and Virtual Journal of Biological Physics Research (April 15, 2005 issue).