Optical Excitations of Chlorophyll a and Chlorophyll b

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Optical Excitations of Chlorophyll a and Chlorophyll b

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Optical Excitations of Chlorophyll a and Chlorophyll b Monomers and Dimers

Journal: Journal of Chemical Theory and Computation

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Manuscript Type: Article

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Complete List of Authors:

Preciado-Rivas, María; Yachay Tech University, School of Physical Sciences and Nanotechnology Mowbray, Duncan; Yachay Tech University, School of Physical Sciences and Nanotechnology Larsen, Ask; Universidad del Pais Vasco, Nano-bio spectroscopy group, Departamento de Fisica de Materiales Milne, Bruce; University of Coimbra, Coimbra Chemistry Center, Department of Chemistry

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56 Optical Excitations of Chlorophyll a and Chlorophyll b

78 Monomers and Dimers

910 María Rosa Preciado-Rivas,† Duncan John Mowbray,∗,†,‡ Ask Hjorth Larsen,‡ and Bruce Forbes Milne ,§,‡

11 † School of Physical Sciences and Nanotechnology, Yachay Tech University, Urcuquí 100119, Ecuador

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‡ Nano-Bio Spectroscopy Group and ETSF Scientific Development Centre, Departamento de Física de Materiales, Universidad del País

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Vasco UPV/EHU, E-20018 San Sebastián, Spain

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Coimbra Chemistry Center, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal

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§ CFisUC, Department of Physics, University of Coimbra, Rua Larga, 3004-516 Coimbra, Portugal

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ABSTRACT: A necessary first step in the development of technologies such as artificial photosynthesis is understanding the photoexcitation

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process within the basic building blocks of naturally-occuring light harvesting complexes (LHCs). The most important of these building

blocks in biological LHCs such as LHC II from green plants are the chlorophyll a (Chl a) and chlorophyll b (Chl b) chromophores dispersed

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throughout the protein matrix. Efforts are still hampered by the lack of economical computational methods that are able to describe optical

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absorption in large biomolecules with sufficient accuracy. In this work we employ a highly efficient localized basis set representation of

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the Kohn–Sham (KS) wave functions at the density functional theory (DFT) level to perform time dependent density functional theory

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(TDDFT) real time and frequency domain calculations of the optical absorption spectra of Chl a and Chl b monomers and dimers. We find

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our TDDFT calculations using linear combinations of atomic orbitals (LCAO) reproduce results obtained with a plane wave (PW) and real

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space (RS) representations of the KS wave functions, but with a significant reduction in computational effort. This work opens the path to

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first principles calculations of optical excitations in macromolecular systems.

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Keywords: chlorophyll, optical excitations, artificial photosynthesis, TDDFT, LCAO, RPA

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1. INTRODUCTION

the Bethe–Salpeter equation (BSE), 29 while often achieving quan-

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titative accuracy, are extremely heavy computationally. 30 As a re-

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Chlorophyll a (Chl a or C55H72MgN4O5) and chlorophyll b (Chl b

sult, only recently have even the smallest dye-sensitized solar cells

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or C55H70MgN4O6), 1,2 depicted schematically in Figure 1, are the

(DSSC) been described at the BSE level. 31 Moreover, such meth-

33 fIuI)n4dpamreesenntatlifnungcretieonnapllaunntist.s oAfsthseuclihg,hutnhdaerrvsetsatnindgincgotmheplpexho(tLoHexC- ondosn-apreeriiondtriicnssyicsatellmy si.ll-suited to the description of isolated and/or

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citation process within Chl a and Chl b is of great importance in

Although TDDFT 20,32 real time 33–36 and frequency domain 37–41

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the development of technologies such as those involved in the op-

calculations provide an attractive alternative, implementations

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timization of food crop production 5,6 and conversion of solar radi-

based on real-space (RS) or plane-wave (PW) representations of

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ation into a usable form of energy directly through methods such

the KS orbitals 27 are both computationally expensive, and exhibit

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as conventional solar cells 7,8 or via subsidiary technologies such as

a strong exchange and correlation (xc) functional dependence for

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photosynthetically-driven (bio)reactor systems for hydrogen com-

their accuracy. For RS calculations, time propagation RS-TDDFT

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bustion. 9–12 Moreover, such information is more generally applica-

calculations require time steps much shorter than what is needed to

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ble to the in silico design and optimization of dye-sensitized solar

resolve the features of the spectra in order to ensure the stability of

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cells, 13 organic photovoltaic cells, 14 photocatalytic systems, 15 op-

the calculation. 25 Such instabilities of RS calculations may be re-

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toelectronic devices, 16 and plasmonics. 17

lated to their freedom in representing the KS wavefunctions, which

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Although much progress has been recently made in both the ex-

are only constrained by the grid spacing.

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perimental measurement of individual monomer and dimer Chl a

In this work we employ linear combinations of atomic orbitals

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and Chl b spectra, 3,18,19 and their theoretical description at the time-

(LCAOs) to provide a more efficient representation of the KS or-

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dependent density functional theory (TDDFT) 20 level, 21–24 the lack

bitals, while retaining the accuracy of RS and PW based TDDFT

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of reasonably accurate yet highly efficient computational methods

real time and frequency domain calculations of the optical ab-

49 hcoasnthaainminpgerbedioemffoolretcsutoleds.esIcnriitbiaeltahteteomptpitcsaltoabinsovrepsttiiognatoeftlhaergoepCtichal-l ssoenrptatitoionn. oFf utrhteheKr,Sthweavcoefnusntrcatiinotnss immapyosbeed ebxypeacnteLdCtAo Oimrperporvee-

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absorption characteristics of biomacromolecules such as the LHC

the stability of time-propagation TDDFT calculations, allowing

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II using first-principles electronic structure methods have helped to

one to use larger time steps. However, the reliability of LCAO-

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clarify several aspects of the functioning of these systems, how-

TDDFT is inherently basis set dependent. 42 This makes an as-

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ever the computational resources required for a complete treatment

sessment and benchmarking for the fundamental functional units

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of systems of this size lie considerably beyond what is generally

with RS-TDDFT or PW-TDDFT essential before applying LCAO-

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available to most researchers. 25,26

TDDFT to the complete macromolecular system. By applying

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On the one hand, methods based on the Kohn–Sham (KS) density

LCAO-TDDFT methods 43,44 to the Chl a and Chl b monomer and

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of states, 27 while being quite efficient, often underestimate energy

dimer systems, we may clearly explain their advantages and disad-

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gaps by more than half. This is because an independent-particle

vantages for describing light-harvesting systems, with the aim of

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picture fails to describe electronic screening of the excited states. 28

applying these methods to macromolecules such as the complete

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On the other hand, quasiparticle-based calculations of spectra from

LHC II. Note that since experimental measurements of the Chl b

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Corresponding Author

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E-mail: [email protected] (D.J.M.).

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Notes

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The authors declare no competing financial interest.

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