Theoretical Investigation of Azo Dyes Adsorbed on Cellulose Fibers

Theoretical Investigation of Azo Dyes Adsorbed on Cellulose Fibers

Electronic Supplementary Material

Theoretical investigation of azo dyes adsorbed on cellulose fibers:

1. Electronic and bonding structures

Farzaneh Zanjanchia, Nasser L. Hadipourb,*, Hassan Sabzyanc, Javad Beheshtiand

a Department of Chemistry, Azad Islamic University of Takestan, P.O. Box 34815-315, Takestan, Islamic Republic of Iran

b Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Islamic Republic of Iran

c Department of Chemistry, University of Isfahan , Isfahan 81764-73441, Islamic Republic of Iran

dDepartment of Chemistry, Shahid Rajaee Teacher Training University, P.O. Box 16875-163, Tehran, Iran

* Corresponding Author: N. L. Hadipour

Phone: +98 21 82883495;

Fax: +98 21 82883455

E-mail address:

/cellulose /cellulose

/cellulose /cellulose

/cellulose /cellulose

Fig. S1Viewed from above of the partially optimized structures of the azo dyes at cellulose crystalline surface obtained at the B3LYP/6-31G** level of theory

Table S1 NBO charges of the O and H atoms for (a) the isolated dyes and (b) the dye/cellulose complexes calculated at the B3LYP/6-31G** level of theory

/
cellulose / /
cellulose / /
cellulose / / / / atom
−0.618 / −0.651 / −0.639 / −0.612 / −0.646 / −0.624 / O2
0.450 / 0.451 / 0.453 / 0.449 / 0.446 / 0.447 / Hα or Hβ
/
cellulose / /
cellulose / /
cellulose / / /
−0.672 / −0.686 / −0.670 / −0.669 / −0.694 / −0.678 / O2
0.512 / 0.511 / 0.520 / 0.512 / 0.509 / 0.511 / Hα or Hβ

Table S2Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the dye

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
17.60 / / 10.05 /
19.24 / / 18.31 /
19.37 / / 56.91 /
18.53 / / 12.74 /
18.33 / / 51.35 /
21.27 / / 11.47 /
35.82 / / 16.02 /
51.76 / / 10.82 /
15.48 / / 16.02 /
505.91a / / 38.85 /
25.32 / / 24.52 /
20.84 / / 11.43 /
18.39 / / 19.04 /
19.81 / / 15.37 /
21.64 / / 19.16 /
41.36 / / 17.59 /

a The largest charge transfer energy for the dye

Table S3Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the dye

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
60.01 / / 222.02a /
32.86 / / 20.29 /
43.43 / / 27.00 /
69.12 / / 10.37 /
64.83 / / 79.67 /
11.63 / / 10.45 /
19.46 / / 15.58 /
15.74 / / 10.76 /
16.96 / / 24.88 /
19.22 / / 22.29 /
16.65 / / 27.64 /
16.31 / / 50.80 /
19.29 / / 66.69 /
17.53 / / 39.66 /
15.11 / / 18.69 /
20.52 / / 18.44 /
27.29 / / 44.09 /
13.85 / / 81.00 /
10.82 / / 61.03 /
34.63 / / 144.80 /
42.68 / / 31.20 /
61.11 /

a The largest charge transfer energy for the dye

Table S4Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the dye

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
76.70 / / 17.09 /
76.96a / / 10.63 /
33.92 / / 52.86 /
48.31 / / 46.02 /
60.28 / / 11.94 /
58.39 / / 10.92 /
15.41 / / 16.10 /
10.44 / / 22.81 /
16.26 / / 25.14 /
32.01 / / 12.77 /
14.98 / / 18.21 /
18.17 / / 19.99 /
28.65 / / 19.61 /
12.41 / / 22.31 /
35.06 / / 20.59 /
48.87 / / 17.12 /
11.88 / / 19.92 /
11.80 / / 21.77 /
11.16 / / 28.84 /
13.81 / / 43.72 /

a The largest charge transfer energy for the dye

Table S5Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the dye

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
18.25 / / 28.81 /
17.86 / / 157.52 /
16.00 / / 11.92 /
16.09 / / 19.43 /
18.40 / / 170.16 /
18.13 / / 42.71 /
17.43 / / 29.24 /
16.37 / / 10.53 /
19.36 / / 18.76 /
20.48 / / 42.43 /
19.64 / / 12.04 /
20.38 / / 401.47a /
21.21 / / 19.27 /
19.75 / / 20.66 /
29.61 / / 12.97 /
14.63 /

a The largest charge transfer energy for the dye

Table S6Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the dye

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
217.81 / / 43.45 /
17.86 / / 29.62 /
215.26 / / 23.55 /
65.57 / / 13.64 /
19.42 / / 19.55 /
19.70 / / 18.79 /
25.14 / / 40.47 /
18.76 / / 11.99 /
10.92 / / 395.28a /
19.53 / / 18.94 /
15.29 / / 18.73 /
17.39 / / 13.42 /
19.05 / / 14.76 /
16.79 / / 18.10 /
16.13 / / 18.38 /
19.17 / / 16.22 /
18.18 / / 15.28 /
14.30 / / 17.50 /
21.89 / / 17.02 /
27.69 / / 17.89 /
16.01 / / 21.26 /
28.36 / / 17.86 /

a The largest charge transfer energy for the dye

Table S7Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the dye

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
21.02 / / 31.88 /
18.73 / / 11.33 /
16.86 / / 129.72 /
20.50 / / 136.03 /
154.60 / / 19.48 /
248.35 / / 44.76 /
27.47 / / 11.59 /
11.03 / / 30.97 /
54.14 / / 18.68 /
19.77 / / 43.67 /
368.99a / / 11.99 /
14.02 / / 399.67a /
16.70 / / 19.07 /
32.34 / / 21.43 /
14.31 / / 12.78 /
18.61 / / 14.56 /
29.46 / / 18.32 /
10.14 / / 17.72 /
12.07 / / 15.98 /
10.28 / / 16.39 /
13.98 / / 18.58 /
129.96 / / 18.62 /
11.97 / / 17.34 /
87.80 / / 15.00 /
13.72 / / 17.63 /
29.44 / / 25.70 /

a The largest charge transfer energy for the dye

Table S8Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the /cellulose complex

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
18.44 / / 10.11 /
47.09 / / 18.61 /
76.08 / / 293.58a /
61.12 / / 23.36 /
31.67 / / 53.85 /
62.91 / / 12.11 /
78.32 / / 15.31 /
81.85 / / 10.80 /
33.12 / / 19.59 /
47.46 / / 24.60 /
66.67 / / 27.09 /
66.21 / / 42.77 /
33.38 / / 19.28 /
44.95 / / 49.53 /
63.94 /

a The largest charge transfer energy for the /cellulose complex

Table S9Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the /cellulose complex

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
34.10 / / 257.97a /
46.10 / / 20.20 /
65.30 / / 26.15 /
64.50 / / 66.93 /
11.96 / / 11.23 /
12.77 / / 15.24 /
15.08 / / 10.60 /
19.44 / / 22.51 /
19.53 / / 23.26 /
17.89 / / 27.64 /
16.51 / / 50.07 /
16.30 / / 65.81 /
12.35 / / 40.54 /
18.05 / / 18.89 /
20.09 / / 18.60 /
29.01 / / 45.10 /
18.00 / / 79.64 /
12.77 / / 60.98 /
43.48 / / 32.16 /
13.43b / / 118.79 /
35.52 / / 61.43 /
45.56 / / 66.82 /

a The largest charge transfer energy for the /cellulose complex

bThe charge transfer energy between the dye and cellulose

Table S10Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the /cellulose complex

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
78.20 / / 10.29 /
80.07a / / 17.16 /
34.23 / / 10.57 /
48.04 / / 51.50 /
61.12 / / 45.64 /
59.22 / / 11.86 /
14.81 / / 16.02 /
17.95 / / 10.94 /
29.23 / / 22.51 /
11.02 / / 25.56 /
10.68 / / 12.58 /
18.75 / / 18.62 /
25.81 / / 19.56 /
13.84 / / 19.83 /
12.15 / / 22.98 /
11.75 / / 20.55 /
11.37 / / 17.16 /
14.01 / / 19.74 /
34.45 / / 21.70 /
48.20 / / 40.55 /
20.05b / / 28.95 /

a The largest charge transfer energy for the /cellulose complex

bThe charge transfer energy between the dye and cellulose

Table S11Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the /cellulose complex

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
58.89 / / 113.52 /
39.10 / / 1018.98a /
18.34 / / 17.43 /
17.44 / / 10.24 /
43.51 / / 29.22 /
55.70 / / 42.96 /
16.28 / / 18.26 /
19.11 / / 78.58 /
20.66 / / 10.04 /
59.07 / / 11.83 /
20.07 / / 392.68 /
21.16 / / 18.95 /
20.96 / / 48.60 /
19.23 / / 32.06 /
29.36 / / 59.96 /

a The largest charge transfer energy for the /cellulose complex.

Table S12Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the /cellulose complex

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
239.77 / / 24.38 /
49.81 / / 12.89 /
20.23 / / 235.99 /
49.64 / / 47.23 /
61.82 / / 43.15 /
11.49 / / 27.11 /
18.93 / / 18.72 /
16.74 / / 41.64 /
16.28 / / 12.00 /
19.67 / / 397.38a /
17.36 / / 19.07 /
17.11 / / 19.35 /
17.05 / / 33.00 /
17.04 / / 58.15 /
17.32 / / 63.86 /
10.10 / / 36.34 /
13.40 / / 128.80 /
19.59 / / 16.94 /
27.27 / / 18.54 /
19.84 / / 43.21 /
10.28b / / 57.50 /
15.30b / / 54.27 /
82.85 / / 18.97 /
29.03 / / 17.79 /

a The largest charge transfer energy for the /cellulose complex.

bThe charge transfer energy between the and cellulose.

Table S13Charge transfer energies between NBO donors and acceptors, , having values larger than 10 kcal/mol obtained for the B3LYP/6-31G** optimized structure of the/cellulose complex

/ Donor NBO (i) → Acceptor NBO (j) / / Donor NBO (i) → Acceptor NBO (j)
17.30 / / 131.21 /
62.88 / / 899.82a /
17.15 / / 17.71 /
19.85 / / 12.07 /
157.44 / / 23.23 /
13.65 / / 41.66 /
28.77 / / 18.69 /
17.65 / / 83.78 /
18.70 / / 12.00 /
27.59 / / 400.00 /
12.11 / / 19.12 /
10.32 / / 50.18 /
13.40 / / 31.22 /
10.93 / / 60.55 /
11.38 / / 58.05 /
85.77 / / 40.14 /
13.43 / / 18.45 /
20.87 / / 17.40 /
18.63 / / 45.34 /
29.45 / / 55.04 /
22.86b / / 20.79 /
23.90 /

a The largest charge transfer energy for the /cellulose complex.

bThe charge transfer energy between the dye and cellulose.

1