Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 132, Issue 14, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3327760
Keywords
Hilbert spaces; reaction kinetics; tensors; time resolved spectroscopy
Funding
- National Science Foundation [CHE-0809306]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0809306] Funding Source: National Science Foundation
Ask authors/readers for more resources
Time-resolved spectroscopy that uses more than one incoherent excitation, and thus has multiple periods of time evolution, is becoming more common. A recent example is multiple population-period transient spectroscopy (MUPPETS), which is implemented as a high-order transient grating. In this paper, a formalism is developed to treat these types of incoherent spectroscopy in a manner that parallels the Liouville-pathway formalism used to treat multidimensional coherent spectroscopy. A Hilbert space of incoherent (population) states is defined and general expressions for transition and time-evolution operators acting on these states are derived from the corresponding quantum operators. This formalism describes incoherent experiments that involve an arbitrary number of temporal dimensions in terms of pathways through the Hilbert space. Each pathway is associated with a multiple-time rate-correlation function. Previous work has shown that these multiple-time correlation functions can measure heterogeneity in electronic-relaxation rates. Thus, they are an analog of coherent echo experiments, which measure heterogeneity in frequencies. We show that similar MUPPETS echo experiments can be done on any incoherent variable. For a dilute molecular solute, the Hilbert-space method leads to a systematic treatment of multidimensional transient gratings. The extension of irreducible-tensor methods to the incoherent Hilbert space results in a classification of orientational gratings of arbitrary order. The general methods developed in this paper are applied more specifically to single-photon, dipole transitions in the following paper.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available