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Title: Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model

Abstract

We recently outlined an efficient multi-tiered parallel ab initio excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground and excited state energies and gradients of large supramolecular complexes in atomistic detail – enabling us to undertake non-adiabatic simulations which explicitly account for the coupled anharmonic vibrational motion of all the constituent atoms in a supramolecular system. Here we apply that framework to the 27 coupled bacterio-chlorophyll-a chromophores which make up the LH2 complex, using it to compute an on-the-fly nonadiabatic surface-hopping (SH) trajectory of electronically excited LH2. Part one of this article is focussed on calibrating our ab initio exciton Hamiltonian using two key parameters: a shift δ, which corrects for the error in TDDFT vertical excitation energies; and an effective dielectric constant ε, which describes the average screening of the transition-dipole coupling between chromophores. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, we tune the values of both δ and ε through fitting to the thermally broadened experimental absorption spectrum, giving a linear absorption spectrum that agrees reasonably well with experiment. In part two of this article, we construct a time-resolved picture of the coupled vibrational and excitation energy transfer (EET) dynamicsmore » in the sub-picosecond regime following photo-excitation. Assuming Franck–Condon excitation of a narrow eigenstate band centred at 800 nm, we use surface hopping to follow a single nonadiabatic dynamics trajectory within the full eigenstate manifold. Consistent with experimental data, this trajectory gives timescales for B800→B850 population transfer (τ B800→B850) between 650–1050 fs, and B800 population decay (τ 800→) between 10–50 fs. The dynamical picture that emerges is one of rapidly fluctuating LH2 eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the atomic vibrations of the constituent chromophores. The eigenstate fluctuations arise from disorder that is driven by vibrational dynamics with multiple characteristic timescales. The scalability of our ab initio excitonic computational framework across massively parallel architectures opens up the possibility of addressing a wide range of questions, including how specific dynamical motions impact both the pathways and efficiency of electronic energy-transfer within large supramolecular systems.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [5];  [6];  [7];  [2]; ORCiD logo [4]; ORCiD logo [1]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States)
  2. Univ. of Bristol (United Kingdom). School of Chemistry
  3. Univ. of Bristol (United Kingdom). School of Chemistry, School of Biochemistry
  4. Univ. of Bristol (United Kingdom). School of Chemistry, Dept. of Computer Science
  5. Univ. of Bristol (United Kingdom). Dept. of Computer Science
  6. Univ. of California, San Francisco, CA (United States). California Inst. for Quantitative Biosciences (QB3), Dept. of Bioengineering and Therapeutic Sciences
  7. City College of New York, NY (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1369335
Grant/Contract Number:  
AC02-76SF00515; ACI-1429830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 23; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sisto, Aaron, Stross, Clem, van der Kamp, Marc W., O’Connor, Michael, McIntosh-Smith, Simon, Johnson, Graham T., Hohenstein, Edward G., Manby, Fred R., Glowacki, David R., and Martinez, Todd J.. Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model. United States: N. p., 2017. Web. doi:10.1039/c7cp00492c.
Sisto, Aaron, Stross, Clem, van der Kamp, Marc W., O’Connor, Michael, McIntosh-Smith, Simon, Johnson, Graham T., Hohenstein, Edward G., Manby, Fred R., Glowacki, David R., & Martinez, Todd J.. Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model. United States. doi:10.1039/c7cp00492c.
Sisto, Aaron, Stross, Clem, van der Kamp, Marc W., O’Connor, Michael, McIntosh-Smith, Simon, Johnson, Graham T., Hohenstein, Edward G., Manby, Fred R., Glowacki, David R., and Martinez, Todd J.. Tue . "Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model". United States. doi:10.1039/c7cp00492c. https://www.osti.gov/servlets/purl/1369335.
@article{osti_1369335,
title = {Atomistic non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model},
author = {Sisto, Aaron and Stross, Clem and van der Kamp, Marc W. and O’Connor, Michael and McIntosh-Smith, Simon and Johnson, Graham T. and Hohenstein, Edward G. and Manby, Fred R. and Glowacki, David R. and Martinez, Todd J.},
abstractNote = {We recently outlined an efficient multi-tiered parallel ab initio excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground and excited state energies and gradients of large supramolecular complexes in atomistic detail – enabling us to undertake non-adiabatic simulations which explicitly account for the coupled anharmonic vibrational motion of all the constituent atoms in a supramolecular system. Here we apply that framework to the 27 coupled bacterio-chlorophyll-a chromophores which make up the LH2 complex, using it to compute an on-the-fly nonadiabatic surface-hopping (SH) trajectory of electronically excited LH2. Part one of this article is focussed on calibrating our ab initio exciton Hamiltonian using two key parameters: a shift δ, which corrects for the error in TDDFT vertical excitation energies; and an effective dielectric constant ε, which describes the average screening of the transition-dipole coupling between chromophores. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, we tune the values of both δ and ε through fitting to the thermally broadened experimental absorption spectrum, giving a linear absorption spectrum that agrees reasonably well with experiment. In part two of this article, we construct a time-resolved picture of the coupled vibrational and excitation energy transfer (EET) dynamics in the sub-picosecond regime following photo-excitation. Assuming Franck–Condon excitation of a narrow eigenstate band centred at 800 nm, we use surface hopping to follow a single nonadiabatic dynamics trajectory within the full eigenstate manifold. Consistent with experimental data, this trajectory gives timescales for B800→B850 population transfer (τB800→B850) between 650–1050 fs, and B800 population decay (τ800→) between 10–50 fs. The dynamical picture that emerges is one of rapidly fluctuating LH2 eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the atomic vibrations of the constituent chromophores. The eigenstate fluctuations arise from disorder that is driven by vibrational dynamics with multiple characteristic timescales. The scalability of our ab initio excitonic computational framework across massively parallel architectures opens up the possibility of addressing a wide range of questions, including how specific dynamical motions impact both the pathways and efficiency of electronic energy-transfer within large supramolecular systems.},
doi = {10.1039/c7cp00492c},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 23,
volume = 19,
place = {United States},
year = {Tue Mar 28 00:00:00 EDT 2017},
month = {Tue Mar 28 00:00:00 EDT 2017}
}

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