State preparation and excited electronic and vibrational behavior in hemes.

State preparation and excited electronic and vibrational behavior in hemes. Research Abstract Details 

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State preparation and excited electronic and vibrational behavior in hemes. Abstract Text:

J Reddy Challa,Tissa C Gunaratne,M Cather Simpson,

The temporally overlapping, ultrafast electronic and vibrational dynamics of a model five-coordinate, high-spin heme in a nominally isotropic solvent environment has been studied for the first time with three complementary ultrafast techniques: transient absorption, time-resolved resonance Raman Stokes, and time-resolved resonance Raman anti-Stokes spectroscopies. Vibrational dynamics associated with an evolving ground-state species dominate the observations. Excitation into the blue side of the Soret band led to very rapid S2 --> S1 decay (sub-100 fs), followed by somewhat slower (800 fs) S1 --> S0 nonradiative decay. The initial vibrationally excited, non-Boltzmann S0 state was modeled as shifted to lower energy by 300 cm(-1) and broadened by 20%. On a approximately 10 ps time scale, the S0 state evolved into its room-temperature, thermal distribution S0 profile largely through VER. Anti-Stokes signals disappear very rapidly, indicating that the vibrational energy redistributes internally in about 1-3 ps from the initial accepting modes associated with S1 --> S0 internal conversion to the rest of the macrocycle. Comparisons of anti-Stokes mode intensities and lifetimes from TRARRS studies in which the initial excited state was prepared by ligand photolysis [Mizutani, T.; Kitagawa, T. Science 1997, 278, 443, and Chem. Rec. 2001, 1, 258] suggest that, while transient absorption studies appear to be relatively insensitive to initial preparation of the electronic excited state, the subsequent vibrational dynamics are not. Direct, time-resolved evaluation of vibrational lifetimes provides insight into fast internal conversion in hemes and the pathways of subsequent vibrational energy flow in the ground state. The overall similarity of the model heme electronic dynamics to those of biological systems may be a sign that the protein's influence upon the dynamics of the heme active site is rather subtle.

State preparation and excited electronic and vibrational behavior in hemes. Publishing Authors By Initials

JR Challa,TC Gunaratne,MC Simpson,

For similar biomechanics: vibration research abstracts see: biomechanics: vibration research

PUBMED ID PMID:

MEDLINE DATE:

State preparation and excited electronic and vibrational behavior in hemes. Journal Published:

PUBLICATION TYPE: Research Support, Non-U.S. Gov

Journal: The journal of physical chemistry. B

VOLUME: 110

Page Numbers: 19956-65

Journal Abbreviation:

ISSN: 1520-6106

DAY: 12

MONTH: Oct

YEAR: 2006

State preparation and excited electronic and vibrational behavior in hemes. Information

Number of References:

LANGUAGE: eng

NlmUniqueID: 101157530

State preparation and excited electronic and vibrational behavior in hemes. Keywords Mesh Terms:

KEYWORDS: Vibration

MESH TERMS: methods

Chemical & Substance for Abstract: State preparation and excited electronic and vibrational behavior in hemes. Information

Substance Name: Heme

Registry Number: 14875-96-8

Grant and Affiliation Information for State preparation and excited electronic and vibrational behavior in hemes.

AFFILIATION: Center for Chemical Dynamics, Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM056816

ACRONYM: GM

MEDLINETA: J Phys Chem B

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