Relaxation, vibrational experimental techniques

The use of computer simulations to study internal motions and thermodynamic properties is receiving increased attention. One important use of the method is to provide a more fundamental understanding of the molecular information contained in various kinds of experiments on these complex systems. In the first part of this paper we review recent work in our laboratory concerned with the use of computer simulations for the interpretation of experimental probes of molecular structure and dynamics of proteins and nucleic acids. The interplay between computer simulations and three experimental techniques is emphasized (1) nuclear magnetic resonance relaxation spectroscopy, (2) refinement of macro-molecular x-ray structures, and (3) vibrational spectroscopy. The treatment of solvent effects in biopolymer simulations is a difficult problem. It is not possible to study systematically the effect of solvent conditions, e.g. added salt concentration, on biopolymer properties by means of simulations alone. In the last part of the paper we review a more analytical approach we have developed to study polyelectrolyte properties of solvated biopolymers. The results are compared with computer simulations. 

The next two chapters are devoted to ultrafast radiationless transitions. In Chapter 5, the generalized linear response theory is used to treat the non-equilibrium dynamics of molecular systems. This method, based on the density matrix method, can also be used to calculate the transient spectroscopic signals that are often monitored experimentally. As an application of the method, the authors present the study of the interfadal photo-induced electron transfer in dye-sensitized solar cell as observed by transient absorption spectroscopy. Chapter 6 uses the density matrix method to discuss important processes that occur in the bacterial photosynthetic reaction center, which has congested electronic structure within 200-1500cm 1 and weak interactions between these electronic states. Therefore, this biological system is an ideal system to examine theoretical models (memory effect, coherence effect, vibrational relaxation, etc.) and techniques (generalized linear response theory, Forster-Dexter theory, Marcus theory, internal conversion theory, etc.) for treating ultrafast radiationless transition phenomena. 

With few exceptions, the experimental techniques that have been devised to study molecular vibrational and rotational energy transfer depend on the measurement of a relaxation time for a gas that is disturbed from its equilibrium condition. In the simplest case, one need consider only a single excitation mechanism in a pure two-state gas ... 

Other experimental techniques have been used to study the very fast relaxation of dye molecules in solution. Ricard and Ducuing studied rhodamine molecules in various solvents and observed vibrational rates ranging from 1 to 4 ps for the first excited singlet state. Their experiment consisted of two pulses with a variable delay time between them the first excites molecules into the excited state manifold and the second measures the time evolution of stimulated emission for different wavelengths. Ricard found a correlation between fast internal conversion and vibrational relaxation rates. Laubereau et al. found a relaxation time of 1.3 0.3 ps for coumarin 6 in CCI4. They used an infrared pulse to prepare a well-defined vibrational mode in the ground electronic state, and monitored the population evolution with a second pulse that excited the system to the lowest singlet excited state, followed by fluorescence detection. 

I shall first discuss briefly the experimental techniques Involved. I shall then review the effects of bond dissociation anharmonlclty in a diatomic molecule. Next I shall introduce the idea of local modes with a simple classical model, and then extend this to a mathematically defined quantum mechanical model which I shall discuss in detail for the case of two symmetry related stretching vibrations, as in the water molecule. I shall then introduce the effects of Fermi resonance, and describe some of our recent work on the dlchloromethane molecule. I shall also describe similar fits to the overtones of carbonyl stretching vibrations in metal carbonyls. Finally I shall comment briefly on the implications of this work for intramolecular vibrational relaxation (IVR) and chemical dynamics. 

The process of vibrational excitation and deexcitation of a diatom in a collision with an atom represents a simplest example from the host of processes which are relevant to gas-phase chemical kinetics. Experimental techniques available now allow one to measure directly state-to-state energy transfer rate coefficients. Theoretically, it is possible to accomplish completely ab initio calculation of these coefficients. One can therefore, regard the existing models of the vibrational relaxation from a new standpoint as a means for helping to understand more clearly the dynamics of the energy transfer provided that all the models are related to a single fundamental principle. This is the Ehrenfest adiabatic principle as formulated by Landau and Teller in the application to the collisional vibrational transitions of diatomic molecules. 

The fast desorption of CO in CO/Cu(OOf) has been measured [33] and also calculated. [30,31] The collision induced vibrational excitation and following relaxation of CO on Cu(001) has also been experimentally explored using time-of-flight techniques, and has been analyzed in experiments [34] and theory. [23,32] Our previous treatment of instantaneous electronic de-excitation of CO/Cu(001) after photoexcitation is extended here to include delayed vibrational relaxation of CO/Cu(001) in its ground electronic state. We show results for the density matrix, from calculations with the described numerical procedure for the integrodifferential equations. 

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