Show simple item record

dc.contributor.authorKhurmi, Champak
dc.contributor.authorBerg, Mark
dc.date.accessioned2019-04-11T05:28:05Z
dc.date.available2019-04-11T05:28:05Z
dc.date.issued2008
dc.date.modified2014-08-19T04:42:53Z
dc.identifier.issn0021-9606
dc.identifier.doi10.1063/1.2960589
dc.identifier.urihttp://hdl.handle.net/10072/62532
dc.description.abstractWe have recently shown that homogeneous and heterogeneous kinetics can be distinguished by experiments that compare the evolution of the population of a state over two time intervals [E. van Veldhoven et al., ChemPhysChem 8, 1761 (2007)]. This paper elaborates on the analogy between these multiple population-period transient spectroscopy (MUPPETS) experiments and more familiar spectroscopies based on the evolution of coherences. Using a modified inverse-Laplace transform, a standard kinetics decay is re-expressed as a “rate spectrum.” A nonexponential decay creates a linewidth in this spectrum. Mechanisms for line broadening in rate spectra are compared to those for line broadening in frequency-domain spectra. Homogeneous and heterogeneous kinetics are defined precisely and are shown to be the counterparts of homogeneous and inhomogeneous line broadenings in frequency-domain spectra. Homogeneous line broadening mechanisms are further divided into equilibrium and nonequilibrium mechanisms, with equilibrium mechanisms more prevalent in frequency spectra and nonequilibrium mechanisms more prevalent in rate spectra. Spectral representations of two-dimensional MUPPETS experiments are developed that are equivalent to two-dimensional coherence spectroscopies. In particular, spectra equivalent to hole-burning and to correlation spectra are defined. Frequency-domain spectra are often modeled as an inhomogeneous distribution of identical homogeneous line shapes. A parallel homogeneous-heterogeneous model for kinetics is defined. Within this model, MUPPETS has sufficient information to completely separate the homogeneous and heterogeneous contributions to a nonexponential decay, even when the homogeneous contribution is nonexponential.
dc.description.peerreviewedYes
dc.description.publicationstatusYes
dc.languageEnglish
dc.language.isoeng
dc.publisherAmerican Institute of Physics
dc.publisher.placeUnited States
dc.relation.ispartofstudentpublicationN
dc.relation.ispartofpagefrom064504-1
dc.relation.ispartofpageto064504-17
dc.relation.ispartofissue6
dc.relation.ispartofjournalJournal of Chemical Physics
dc.relation.ispartofvolume129
dc.rights.retentionY
dc.subject.fieldofresearchPhysical Sciences not elsewhere classified
dc.subject.fieldofresearchPhysical Sciences
dc.subject.fieldofresearchChemical Sciences
dc.subject.fieldofresearchEngineering
dc.subject.fieldofresearchcode029999
dc.subject.fieldofresearchcode02
dc.subject.fieldofresearchcode03
dc.subject.fieldofresearchcode09
dc.titleParallels between multiple population-period transient spectroscopy and multidimensional coherence spectroscopies
dc.typeJournal article
dc.type.descriptionC1 - Articles
dc.type.codeC - Journal Articles
gro.hasfulltextNo Full Text
gro.griffith.authorKhurmi, Champak


Files in this item

FilesSizeFormatView

There are no files associated with this item.

This item appears in the following Collection(s)

  • Journal articles
    Contains articles published by Griffith authors in scholarly journals.

Show simple item record