Structural dynamics of a catalytic monolayer probed by ultrafast 2D IR vibrational echoes.

نویسندگان

  • Daniel E Rosenfeld
  • Zsolt Gengeliczki
  • Brian J Smith
  • T D P Stack
  • M D Fayer
چکیده

Ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy has proven broadly useful for studying molecular dynamics in solutions. Here, we extend the technique to probing the interfacial dynamics and structure of a silica surface-tethered transition metal carbonyl complex--tricarbonyl (1,10-phenanthroline)rhenium chloride--of interest as a photoreduction catalyst. We interpret the data using a theoretical framework devised to separate the roles of structural evolution and excitation transfer in inducing spectral diffusion. The structural dynamics, as reported on by a carbonyl stretch vibration of the surface-bound complex, have a characteristic time of ~150 picoseconds in the absence of solvent, decrease in duration by a factor of three upon addition of chloroform, and decrease another order of magnitude for the bulk solution. Conversely, solvent-complex interactions increase the lifetime of the probed vibration by 160% when solvent is applied to the monolayer.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Structural Dynamics at Monolayer−Liquid Interfaces Probed by 2D IR Spectroscopy

Monolayers functionalized with tricarbonyl1,10-phenanthroline rhenium chloride (RePhen(CO)3Cl) are studied in the presence of a variety of polar organic solvents (chloroform, tetrahydrofuran, dimethylformamide, acetonitrile), hexadecane, and water. The headgroup, RePhen(CO)3Cl, is soluble in the bulk polar organic solvents but not in hexadecane or water. The surface structural dynamics are stud...

متن کامل

Structural dynamics inside a functionalized metal-organic framework probed by ultrafast 2D IR spectroscopy.

The structural elasticity of metal-organic frameworks (MOFs) is a key property for their functionality. Here, we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants ...

متن کامل

Size-dependent ultrafast structural dynamics inside phospholipid vesicle bilayers measured with 2D IR vibrational echoes.

The ultrafast structural dynamics inside the bilayers of dilauroylphosphatidylcholine (DLPC) and dipalmitoylphosphatidylcholine vesicles with 70, 90, and 125 nm diameters were directly measured with 2D IR vibrational echo spectroscopy. The antisymmetric CO stretch of tungsten hexacarbonyl was used as a vibrational probe and provided information on spectral diffusion (structural dynamics) in the...

متن کامل

Disulfide bond influence on protein structural dynamics probed with 2D-IR vibrational echo spectroscopy.

Intramolecular disulfide bonds are understood to play a role in regulating protein stability and activity. Because disulfide bonds covalently link different components of a protein, they influence protein structure. However, the effects of disulfide bonds on fast (subpicosecond to approximately 100 ps) protein equilibrium structural fluctuations have not been characterized experimentally. Here,...

متن کامل

Intermolecular vibrational energy exchange directly probed with ultrafast two dimensional infrared spectroscopy.

Ultrafast two dimensional infrared (2D IR) spectroscopy has been applied to probe the intermolecular vibrational energy exchange between two model molecules, benzonitrile and acetonitrile-(d3). The vibrational energy exchange between these two molecules is manifested through the growth of cross peaks in their 2D IR spectra. In experiments, their nitrile groups (CN) are not involved in the energ...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Science

دوره 334 6056  شماره 

صفحات  -

تاریخ انتشار 2011