TY - JOUR
T1 - Influence of Hydrogen Bonds on the Electron-Phonon Coupling Strength/Marker Mode Structure and Charge Separation Rates in Reaction Centers from Rhodobacter sphaeroides
AU - Khmelnitskiy, Anton
AU - Williams, Jo Ann C.
AU - Allen, James P.
AU - Jankowiak, Ryszard
N1 - Funding Information:
This work was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (Grant No. DE-SC0006678 to R.J.) and National Science Foundation (CHE-1904860 to J.P.A. and J.C.W.). We acknowledge assistance with the reaction center preparations by Eduardo Espiritu and Kori Chamberlain.
Funding Information:
This work was supported by the Chemical Sciences Geosciences and Biosciences Division, Office of Basic Energy Sciences Office of Science, U.S. Department of Energy (Grant No. DE-SC0006678 to R.J.) and National Science Foundation (CHE-1904860 to J.P.A. and J.C.W.). We acknowledge assistance with the reaction center preparations by Eduardo Espiritu and Kori Chamberlain.*%blankline%*
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/10/17
Y1 - 2019/10/17
N2 - Low-temperature persistent and transient hole-burning (HB) spectra are presented for the triple hydrogen-bonded L131LH + M160LH + M197FH mutant of Rhodobacter sphaeroides. These spectra expose the heterogeneous nature of the P-, B-, and H-bands, consistent with a distribution of electron transfer (ET) times and excitation energy transfer (EET) rates. Transient P+QA - holes are observed for fast (tens of picoseconds or faster) ET times and reveal strong coupling to phonons and marker mode(s), while the persistent holes are bleached in a fraction of reaction centers with long-lived excited states characterized by much weaker electron-phonon coupling. Exposed differences in electron-phonon coupling strength, as well as a different coupling to the marker mode(s), appear to affect the ET times. Both resonantly and nonresonantly burned persistent HB spectra show weak blue-(âˆ150 cm-1) and large, red-shifted (âˆ300 cm-1) antiholes of the P band. Slower EET times from the H- A nd B-bands to the special pair dimer provide new insight on the influence of hydrogen bonds on mutation-induced heterogeneity.
AB - Low-temperature persistent and transient hole-burning (HB) spectra are presented for the triple hydrogen-bonded L131LH + M160LH + M197FH mutant of Rhodobacter sphaeroides. These spectra expose the heterogeneous nature of the P-, B-, and H-bands, consistent with a distribution of electron transfer (ET) times and excitation energy transfer (EET) rates. Transient P+QA - holes are observed for fast (tens of picoseconds or faster) ET times and reveal strong coupling to phonons and marker mode(s), while the persistent holes are bleached in a fraction of reaction centers with long-lived excited states characterized by much weaker electron-phonon coupling. Exposed differences in electron-phonon coupling strength, as well as a different coupling to the marker mode(s), appear to affect the ET times. Both resonantly and nonresonantly burned persistent HB spectra show weak blue-(âˆ150 cm-1) and large, red-shifted (âˆ300 cm-1) antiholes of the P band. Slower EET times from the H- A nd B-bands to the special pair dimer provide new insight on the influence of hydrogen bonds on mutation-induced heterogeneity.
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U2 - 10.1021/acs.jpcb.9b08388
DO - 10.1021/acs.jpcb.9b08388
M3 - Article
C2 - 31539255
AN - SCOPUS:85073110740
SN - 1520-6106
VL - 123
SP - 8717
EP - 8726
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 41
ER -