Two-color pump-probe spectroscopies of two- and three-level systems

2-dimensional line shapes and solvation dynamics

Kijeong Kwac, Minhaeng Cho

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

For both two- and three-level systems, theoretical descriptions of two-color transient grating, transient dichroism, and transient birefringence spectroscopies were presented. The two-dimensional line shapes of these pump-probe spectra were found to be strongly dependent on the solvation dynamics. The two-dimensional contours of the transient birefringence signal of a two-level system are not vertically directed in the short time region. The inverse slope of the tangential line of the two-dimensional contours was found to be linearly proportional to the solvation correlation function. The two-dimensional transient grating and dichroism spectra are shown to directly provide quantitative information on the reorganization energy and spectral diffusion dynamics. For a three-level system that is a model for an anharmonic oscillator, the peak separation observed in a two-dimensional transient dichroism spectrum was found to be determined by both fluctuation amplitude of the transition frequency and spectral bandwidth of the probe pulse. The transient dichroism and birefringence contours of a three-level system were also found to be tilted in the short time region. We, in the present paper, established a variety of relationships between two-dimensional pump-probe line shapes and solvation correlation function.

Original languageEnglish
Pages (from-to)5903-5912
Number of pages10
JournalJournal of Physical Chemistry A
Volume107
Issue number31
DOIs
Publication statusPublished - 2003 Aug 7

Fingerprint

Birefringence
Solvation
solvation
line shape
Spectrum Analysis
Color
dichroism
Pumps
Spectroscopy
pumps
color
probes
birefringence
spectroscopy
gratings (spectra)
Dichroism
oscillators
gratings
slopes
bandwidth

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Two-color pump-probe spectroscopies of two- and three-level systems : 2-dimensional line shapes and solvation dynamics. / Kwac, Kijeong; Cho, Minhaeng.

In: Journal of Physical Chemistry A, Vol. 107, No. 31, 07.08.2003, p. 5903-5912.

Research output: Contribution to journalArticle

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