Diffusion spectral

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VIBRATIONAL LINE SHAPES, SPECTRAL DIFFUSION, AND HYDROGEN BONDING IN LIQUID WATER... 

Vibrational spectroscopy can help us escape from this predicament due to the exquisite sensitivity of vibrational frequencies, particularly of the OH stretch, to local molecular environments. Thus, very roughly, one can think of the infrared or Raman spectrum of liquid water as reflecting the distribution of vibrational frequencies sampled by the ensemble of molecules, which reflects the distribution of local molecular environments. This picture is oversimplified, in part as a result of the phenomenon of motional narrowing The vibrational frequencies fluctuate in time (as local molecular environments rearrange), which causes the line shape to be narrower than the distribution of frequencies [3]. Thus in principle, in addition to information about liquid structure, one can obtain information about molecular dynamics from vibrational line shapes. In practice, however, it is often hard to extract this information. Recent and important advances in ultrafast vibrational spectroscopy provide much more useful methods for probing dynamic frequency fluctuations, a process often referred to as spectral diffusion. Ultrafast vibrational spectroscopy of water has also been used to probe molecular rotation and vibrational energy relaxation. The latter process, while fundamental and important, will not be discussed in this chapter, but instead will be covered in a separate review [4],... 

First, as the molecule on which the chromophore sits rotates, this projection will change. Second, the magnitude of the transition dipole may depend on bath coordinates, which in analogy with gas-phase spectroscopy is called a non-Condon effect For water, as we will see, this latter dependence is very important [13, 14]. In principle there are off-diagonal terms in the Hamiltonian in this truncated two-state Hilbert space, which depend on the bath coordinates and which lead to vibrational energy relaxation [4]. In practice it is usually too difficult to treat both the spectral diffusion and vibrational relaxation problems at the same time, and so one usually adds the effects of this relaxation phenomenologically, and the lifetime 7j can either be calculated separately or determined from experiment. Within this approach the line shape can be written as [92 94]... 

As evidenced from the above discussion, vibrational line shapes provide information mostly about intermolecular structure. Transient hole burning and more recently echo experiments, on the other hand, can provide information about the dynamics of spectral diffusion. The first echo experiments on the HOD/ D2O system involved two excitation pulses, and the signal was detected either by integrating the intensity [20] or by heterodyning [22]. The experiments were analyzed with the standard model assuming Gaussian frequency fluctuations. The data were consistent with a spectral diffusion TCF that was bi-exponential, involving fast and slow times of about 100 fs and 1 ps, respectively. 

Shortly thereafter came reports of integrated three-pulse photon echoes, especially using the echo peak shift to provide information about spectral diffusion [21, 23]. In one experiment [10, 23] the peak shift shows an intriguing oscillation at short times with a period of about 180 fs, followed by a slower relaxation with a decay time of 1.4 ps. The three-pulse echo amplitude can also be heterodyned, leading to 2DIR experiments [24 26]. The latter experiments provide a wealth of information, and there are several ways to extract the desired spectral diffusion dynamics [149]. 

DIR spectra have been obtained by the Fayer group on HOD/H20 [53 55]. They characterize the extent of spectral diffusion by the waiting time dependence... 

It is more difficult to perform ultrafast spectroscopy on neat H20 (than it is on H0D/D20 or HOD/H20) since the neat fluid is so absorptive in the OH stretch region. One innovative and very informative technique, developed by Dlott, involves IR pumping and Raman probing. This technique has a number of advantages over traditional IR pump-probe experiments The scattered light is Stokes-shifted, which is less attenuated by the sample, and one can simultaneously monitor the populations of all Raman-active vibrations of the system at the same time. These experimental have been brought to bear on the spectral diffusion problem in neat water [18, 19, 75 77],... 

We have described our most recent efforts to calculate vibrational line shapes for liquid water and its isotopic variants under ambient conditions, as well as to calculate ultrafast observables capable of shedding light on spectral diffusion dynamics, and we have endeavored to interpret line shapes and spectral diffusion in terms of hydrogen bonding in the liquid. Our approach uses conventional classical effective two-body simulation potentials, coupled with more sophisticated quantum chemistry-based techniques for obtaining transition frequencies, transition dipoles and polarizabilities, and intramolecular and intermolecular couplings. In addition, we have used the recently developed time-averaging approximation to calculate Raman and IR line shapes for H20 (which involves... 

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