Convergence of environment polarization effects in multiscale modeling of excitation energies

Maarten Beerepoot, Arnfinn Hykkerud Steindal, Kenneth Ruud, Jógvan Magnus Haugaard Olsen, Jacob Kongsted

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

We present a systematic investigation of the influence of polarization effects from a surrounding medium on the excitation energies of a chromophore. We use a combined molecular dynamics and polarizable embedding time-dependent density functional theory (PE-TD-DFT) approach for chromophores in proteins and in homogeneous solvents. The mutual polarization between the chromophore and its surroundings is included in the PE-TD-DFT approach through the use of induced dipoles, placed on all atoms in the classical region, and self-consistent optimization of the quantum and classical polarizable regions. By varying the subset of sites in the environment for which atomic polarizabilities are included, we investigate to what distance from the quantum region explicit polarization effects need to be taken into account in order to provide converged excitation energies. Our study gives new insight into the range of polarization interactions for chromophores in different chemical environments. We find that the rate of convergence of excitation energies with respect to polarization cut-off is much slower for chromophores in an ordered environment such as a protein than for chromophores in a homogeneous medium such as a solvent. We show that this in part is related to the (partial) charges in the protein. Our results provide insight into how to define a representation of complex environments of different kinds in an accurate and affordable way.
OriginalsprogEngelsk
TidsskriftComputational and Theoretical Chemistry
Vol/bind1040-1041
Udgave nummerJuly
Sider (fra-til)304-311
ISSN2210-271X
DOI
StatusUdgivet - 2014

Fingeraftryk

Excitation energy
Chromophores
chromophores
Polarization
polarization
excitation
proteins
embedding
Proteins
Density functional theory
energy
Molecular Dynamics Simulation
density functional theory
set theory
Molecular dynamics
cut-off
dipoles
molecular dynamics
Atoms
optimization

Citer dette

Beerepoot, Maarten ; Steindal, Arnfinn Hykkerud ; Ruud, Kenneth ; Olsen, Jógvan Magnus Haugaard ; Kongsted, Jacob. / Convergence of environment polarization effects in multiscale modeling of excitation energies. I: Computational and Theoretical Chemistry. 2014 ; Bind 1040-1041, Nr. July. s. 304-311.
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Convergence of environment polarization effects in multiscale modeling of excitation energies. / Beerepoot, Maarten; Steindal, Arnfinn Hykkerud; Ruud, Kenneth; Olsen, Jógvan Magnus Haugaard; Kongsted, Jacob.

I: Computational and Theoretical Chemistry, Bind 1040-1041, Nr. July, 2014, s. 304-311.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Convergence of environment polarization effects in multiscale modeling of excitation energies

AU - Beerepoot, Maarten

AU - Steindal, Arnfinn Hykkerud

AU - Ruud, Kenneth

AU - Olsen, Jógvan Magnus Haugaard

AU - Kongsted, Jacob

PY - 2014

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AB - We present a systematic investigation of the influence of polarization effects from a surrounding medium on the excitation energies of a chromophore. We use a combined molecular dynamics and polarizable embedding time-dependent density functional theory (PE-TD-DFT) approach for chromophores in proteins and in homogeneous solvents. The mutual polarization between the chromophore and its surroundings is included in the PE-TD-DFT approach through the use of induced dipoles, placed on all atoms in the classical region, and self-consistent optimization of the quantum and classical polarizable regions. By varying the subset of sites in the environment for which atomic polarizabilities are included, we investigate to what distance from the quantum region explicit polarization effects need to be taken into account in order to provide converged excitation energies. Our study gives new insight into the range of polarization interactions for chromophores in different chemical environments. We find that the rate of convergence of excitation energies with respect to polarization cut-off is much slower for chromophores in an ordered environment such as a protein than for chromophores in a homogeneous medium such as a solvent. We show that this in part is related to the (partial) charges in the protein. Our results provide insight into how to define a representation of complex environments of different kinds in an accurate and affordable way.

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DO - 10.1016/j.comptc.2014.03.022

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SN - 2210-271X

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