Monitoring equilibrium reaction dynamics of a nearly barrierless molecular rotor using ultrafast vibrational echoes.

Using rapidly acquired spectral diffusion, a recently developed variation of heterodyne detected infrared photon echo spectroscopy, we observe ∼3 ps solvent independent spectral diffusion of benzene chromium tricarbonyl (C6H6Cr(CO)3, BCT) in a series of nonpolar linear alkane solvents. The spectral dynamics is attributed to low-barrier internal torsional motion. This tripod complex has two stable minima corresponding to staggered and eclipsed conformations, which differ in energy by roughly half of kBT. The solvent independence is due to the relative size of the rotor compared with the solvent molecules, which create a solvent cage in which torsional motion occurs largely free from solvent damping. Since the one-dimensional transition state is computed to be only 0.03 kBT above the higher energy eclipsed conformation, this model system offers an unusual, nearly barrierless reaction, which nevertheless is characterized by torsional coordinate dependent vibrational frequencies. Hence, by studying the spectral diffusion of the tripod carbonyls, it is possible to gain insight into the fundamental dynamics of internal rotational motion, and we find some evidence for the importance of non-diffusive ballistic motion even in the room-temperature liquid environment. Using several different approaches to describe equilibrium kinetics, as well as the influence of reactive dynamics on spectroscopic observables, we provide evidence that the low-barrier torsional motion of BCT provides an excellent test case for detailed studies of the links between chemical exchange and linear and nonlinear vibrational spectroscopy.

Site-specific measurements of lipid membrane interfacial water dynamics with multidimensional infrared spectroscopy.

One route to accessing site-specific dynamical information available with ultrafast multidimensional infrared spectroscopy is the development of robust and versatile vibrational probes. Here we synthesize and characterize a vibrationally labeled cholesterol derivative, (cholesteryl benzoate) chromium tricarbonyl, to probe model lipid membranes, focusing specifically on the membrane-water interface. Utilizing FTIR and polarized-ATR spectroscopies, we determine the location of the chromium tricarbonyl motif to be situated at the water-membrane interface with an orientation of 46 ± 2° relative to the vector normal to the membrane surface. We test the dynamical sensitivity of the (cholesteryl benzoate) chromium tricarbonyl label with two different nonlinear infrared spectroscopy methods, both of which show that the probe is well-suited to the study of membrane dynamics as well as the dynamics of water at the membrane interface. The metal carbonyl vibrational probe located at the surface of a bicelle exhibits spectral diffusion dynamics induced by membrane hydration water that is roughly three times slower than observed using a nearly identical vibrational probe in bulk water.

Ultrafast 2DIR probe of a host-guest inclusion complex: structural and dynamical constraints of nanoconfinement.

Two-dimensional infrared (2DIR) spectroscopy is used to study the influence of nanoconfinement on the spectral diffusion dynamics of cyclopentadienyl manganese tricarbonyl (CpMn(CO)3, CMT) free in solution and confined in the cavity of ß-cyclodextrin. Contrary to the reorientation correlation function of the solvent molecules, determined through molecular dynamics simulations, measurements in three different solvents indicate that CMT confined in ß-cyclodextrin undergoes spectral diffusion that is faster than free CMT. To account for this discrepancy, we propose that spectral diffusion time scales contain a dynamical contribution that is dependent on the effective size of the conformational space presented by the solvation environment. This solvation state space size is related to the number of participating solvent molecules, which in turn is proportional to the solvent accessible surface area (SASA). We test the role of the number of participating solvent molecules using a simple Gaussian-Markov simulation and find that an increase in the number of participating solvent molecules indeed slows the time required to search the available conformational space. Finally, we test this dependence by comparing the spectral diffusion of a previously studied manganese carbonyl, dimanganese decacarbonyl (Mn2(CO)10, DMDC), to CMT and find that DMDC, which has a larger SASA, exhibits slower spectral diffusion. The experimental observations and the supporting simplistic solvation model suggest that vibrational probe molecules, such as CMT, might be able to function as sensors of conformational entropy.

Rapid and accurate measurement of the frequency-frequency correlation function.

Using an implementation of heterodyne-detected vibrational echo spectroscopy, we show that equilibrium spectral diffusion caused by solvation dynamics can be measured in a fraction of the time required using traditional two-dimensional infrared spectroscopy. Spectrally resolved, heterodyne-detected rephasing and nonrephasing signals, recorded at a single delay between the first two pulses in a photon echo sequence, can be used to measure the full waiting time dependent spectral dynamics that are typically extracted from a series of 2D-IR spectra. Hence, data acquisition is accelerated by more than 1 order of magnitude, while permitting extremely fine sampling of the spectral dynamics during the waiting time between the second and third pulses. Using cymantrene (cyclopentadienyl manganese tricarbonyl, CpMn(CO)3) in alcohol solutions, we compare this novel approach--denoted rapidly acquired spectral diffusion (RASD)--with a traditional method using full 2D-IR spectra, finding excellent agreement. Though this approach is largely limited to isolated vibrational bands, we also show how to remove interference from cross-peaks that can produce characteristic modulations of the spectral dynamics through vibrational quantum beats.