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Alexander V. Benderskii

Associate Professor of Chemistry
Physical Chemistry

M.S. 1992 Moscow Institute of Physics and Technology (Russia)
Ph.D. 1996 University of Utah
Office: SSC 602
Phone: (213) 740-3220
Fax: (213) 740-2701
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Research Focus


Laser Spectroscopy of Biological and Material Interfaces

Our research focuses on molecular structure and dynamics of surfaces and interfaces. Two complementary aspects of our research program are (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; and (2) applications of these techniques for studies of molecular structure, organization, reactivity, and dynamics in these interesting and complex environments.

Currently, we are focusing on vibrational spectroscopy (mid-infrared spectral range) because it provides a wealth 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), a broad-band spectral interferometry technique 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 surfaces and interfaces important in life sciences, nano- and bio- technology, and material science. Our 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 water in the interfacial region, in particular 'biological water', a thin layer adjacent to biointerfaces. Using surface-selective spectroscopy, we are systematically investigating how the ultrafast dynamics of the aqueous H-bond network is affected by the chemical functionalities and electrostatics of interfaces. To this end, we investigate the ultrafast vibrational and rotational dynamics of the water molecules themselves as well as carefully chosen small probe molecules at aqueous 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. Another aspect of this project is the exploration of the enhancement of nonlinear spectroscopic signals due to local nanoplasmon effects, with potential application in sensors with ultra-low detection limits and high molecular information content.

Selected publications

1.Malyk, S.; Shalhout, F. Y.; Benderskii, A. V "Vibrational Sum Frequency Spectroscopic Investigation of the Azimuthal Anisotropy and Rotational Dynamics of Methyl-Terminated Silicon(111) Surfaces" J. Phys. Chem. C 117 (2), 935-944 (2013).
2.Vinaykin, M.; Benderskii, A. V. "Vibrational Sum-Frequency Spectrum of the Water Bend at the Air/Water Interface" J. Phys. Chem. Lett., 3 (22), 3348-3352 (2012).
3.Shalhout, F. Y.; Malyk, S.; Benderskii, A. V. "Relative Phase Change of Nearby Resonances in Temporally Delayed Sum Frequency Spectra" J. Phys. Chem. Lett.,3 (23), 3493-3497 (2012).
4.Stiopkin, I.V.; Weeraman, C.; Pieniazek, P. A.; Shalhout, F.Y.; Skinner, J.L.; Benderskii, A. V. "Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy", Nature 474, 192 (2011).
5.Stiopkin, I. V., Jayathilake, H. D.; Benderskii, A. V. "Temporal Effects on Spectroscopic Line Shapes, Resolution, and Sensitivity of the Broad-Band Sum Frequency Generation" J. Chem. Phys. 132,234503, 1-9 (2010).
6.Jayathilake, H.D.; Driscoll, J.; Bordenyuk, A. N.; Wu, L.; da Rocha S. R. P.; Verani, C. N.; Benderskii, A. V. "Molecular Order in Langmuir-Blodgett Monolayers of Metal-Ligand Surfactants Probed by Sum Frequency Generation" Langmuir 25, 6880-6886 (2009).
7.Yatawara, A. K.; Tiruchinapaly, G.; Bordenyuk, A. N.; Andreana, P.R.; Benderskii, A.V. "Carbohydrate Surface Attachment Characterized by Sum Frequency Generation Spectroscopy", Langmuir 25, 1901-1904 (2009).
8.Palyvoda, O.; Bordenyuk, A. N.; Yatawara, A. K.; McCullen, E; Chen, C.-C.; Benderskii, A. V.; Auner, G. W. "Molecular Organization in SAMs Used for Neuronal Cell Growth" Langmuir, 24, 4097 (2008).
9.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).
10.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).
11.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).
12.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).
13.Bordenyuk, A.N.; Jayathilake, H.; Benderskii, A. V. "Coherent Vibrational Quantum Beats as a Probe of Langmuir-Blodgett Monolayers", J. Phys. Chem. B. 10, 15941 - 15949 (2005). Journal Cover Vol. 109, No. 33 (August 25, 2005).
14.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) (11 pages). Also published in: Virtual Journal of Ultrafast Science (May 2005 issue) and Virtual Journal of Biological Physics Research (April 15, 2005 issue).

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