Supporting information

Computational study on the effects of substituent and heteroatom on physical properties and solar cell performance in donor-acceptor conjugated polymers based on Benzodithiophene

Lvyong Zhang, Wei Shen, Rongxing He, Zhiyong Fu,Xiaorui Liu, Ming Li*

School of Chemistry and Chemical Engineering, SouthwestUniversity, Chongqing 400715, PR China

Table S1The HOMO energy level (in eV) of PBSA obtained in gas phase with different functionals and basis sets

Basis set / PBE0 / PBEh1PBE / mPW1PBE
6-31G* / -5.48 / -5.48 / -5.50
6-311G* / -5.65 / -5.65 / -5.66
Exp.(polymer) / -5.56a

a from reference [1]

Table S2The HOMO energy level (in eV) of PBSeA obtained in gas phase with different functionals and basis sets

Basis set / PBE0 / PBEh1PBE / mPW1PBE
6-31G* / -5.47 / -5.47 / -5.48
6-311G* / -5.64 / -5.64 / -5.65
Exp.(polymer) / -5.51a

a from reference [1]

Table S3Calculated Eex(in eV) , λ (in nm) and f of PBSA using three different functionals and fixing basis set at 6-31G* both in gas phase and in chloroform solution

mPW1PBE / B3LYP / O3LYP / Exp.
Eex / λ / f / Eex / λ / f / Eex / λ / f / λ (Eopt)
In gas phase / S1 / 2.44 / 509 / 1.04 / 2.32 / 534 / 0.89 / 2.11 / 587 / 0.45
S2 / 2.63 / 471 / 0.12 / 2.49 / 498 / 0.14 / 2.26 / 548 / 0.31
In chloroform
solution / S1 / 2.39 / 519 / 1.32 / 2.28 / 543 / 1.19 / 2.06 / 592 / 0.74 / 610(2.03)a
550(2.25)a
S2 / 2.64 / 469 / 0.19 / 2.50 / 496 / 0.16 / 2.26 / 548 / 0.31

a from reference [1]

Table S4Calculated Eex (in eV) , λ (in nm) and f of PBSA using three differentbasis sets and fixing functional atO3LYP both in gas phase and in chloroform solution

6-31G* / 6-311G* / 6-311+G* / Exp.
Eex / λ / f / Eex / λ / f / Eex / λ / f / λ (Eopt)
In gas phase / S1 / 2.11 / 587 / 0.45 / 2.09 / 593 / 0.46 / 2.07 / 599 / 0.44
S2 / 2.26 / 548 / 0.31 / 2.23 / 556 / 0.28 / 2.21 / 561 / 0.28
In chloroform
solution / S1 / 2.09 / 592 / 0.74 / 2.08 / 597 / 0.75 / 2.06 / 603 / 0.74 / 610(2.03)a
550(2.25)a
S2 / 2.26 / 548 / 0.31 / 2.24 / 554 / 0.28 / 2.22 / 560 / 0.28

a from reference [1]

Table S5Calculated Eex (in eV) , λ (in nm) and f of PBSeA using three different functionals and fixing basis set at 6-31G* both in gas phase and in chloroform solution

mPW1PBE / B3LYP / O3LYP / Exp.
Eex / λ / f / Eex / λ / f / Eex / λ / f / λ (Eopt)
In gas phase / S1 / 2.38 / 520 / 1.08 / 2.27 / 545 / 0.93 / 2.08 / 597 / 0.51
S2 / 2.58 / 481 / 0.10 / 2.44 / 508 / 0.12 / 2.21 / 560 / 0.28
In chloroform
solution / S1 / 2.34 / 530 / 1.37 / 2.24 / 554 / 1.25 / 2.06 / 602 / 0.82 / 635(1.95)a
565(2.19)a
S2 / 2.59 / 479 / 0.16 / 2.45 / 505 / 0.14 / 2.22 / 560 / 0.28

a from reference [1]

Table S6Calculated Eex (in eV) , λ (in nm) and f of PBSeA using three differentbasis sets and fixing functional at O3LYP both in gas phase and in chloroform solution

mPW1PBE / B3LYP / O3LYP / Exp.
Eex / λ / f / Eex / λ / f / Eex / λ / f / λ (Eopt)
In gas phase / S1 / 2.08 / 597 / 0.51 / 2.05 / 605 / 0.51 / 2.03 / 612 / 0.50
S2 / 2.21 / 560 / 0.28 / 2.18 / 569 / 0.25 / 2.15 / 576 / 0.25
In chloroform
solution / S1 / 2.06 / 602 / 0.82 / 2.04 / 609 / 0.83 / 2.01 / 616 / 0.82 / 635(1.95)a
565(2.19)a
S2 / 2.22 / 560 / 0.28 / 2.19 / 566 / 0.23 / 2.17 / 573 / 0.23

a from reference [1]

Refereces

[1]S Beaupré, A Pron, SH Drouin, et al. (2012) Macromolecules 45: 6906.