LP N to BD* C-C = BD C-C to BD* O-H = LP* C to LP* B =5.

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Ἁλκυόνη Διδώ Αργυριάδης
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1 Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2016 MS No.: CP-ART R1 Optical Response and Gas Sequestration Properties of Metal Cluster Supported Graphene Nanoflakes Debdutta Chakraborty and Pratim Kumar Chattaraj* Department of Chemistry and Centre for Theoretical Studies Indian Institute of Technology, Kharagpur , West Bengal, India * To whom correspondence should be addressed. pkc@chem.iitkgp.ernet.in, Telephone: , Fax: Supplementary Information Table Table S1. Free energy change (ΔG, kcal/mol) and reaction enthalpy change ( H, kcal/mol) at 298K for the process: CO/NO/CH 3 OH + GR/BGR/BNGR CO/NO/GR/BGR/BNGR; ZPE corrected dissociation energy (D 0, kcal/mol) for the dissociation process: CO/NO/GR/BGR/BNGR CO/NO/CH 3 OH + GR/BGR/BNGR; HOMO-LUMO gap (Gap) (in ev), Polarizability ( ) (in a.u. 3 ); most important stabilizing donor-acceptor interaction (E(2)) (in kcal/mol) as given by second order perturbation theory analysis of Fock matrix in the NBO basis for the CO/NO/GR/BGR/BNGR moieties; NBO charges on adsorbate molecules (Q K (Ad)); distance in between the adsorbates and adsorbent (R Ad-Surface ) (in Ǻ); important bond lengths of the CO/NO/CH 3 OH molecules at the adsorbed state on CO/NO/CH 3 (in Ǻ). Systems G H D 0 Gap E(2) Q K (Ad) R Ad- R Ad Surface GR BD C-C to LP* C =0.75 O=- 0.51, C= 0.51 C-C= 3.29 C-O=

2 GR LP N to BD* C-C =0.24 N= 0.21, O= N-C= 3.13 N-O= 1.15 GR BD C-C to BD* O-H =0.78 O=- 0.76, H a =0.49, C=-0.32, H b =0.22, 0.19, 0.19 O-C= 3.26, H a -C= 2.60 O- H a =0.96, C-O= 1.40, C- H b = 1.10 BGR LP* C to LP* B =5.98 O=- 0.51, C= 0.51 C-B= 3.25 C-O= 1.14 BGR LP* B to BD* N-O =16.14 N= 0.24, O= N-B= 2.93 N-O= 1.15 BGR BD C-C to BD* O-H =1.19 O=- 0.77, H a =0.50, C=-0.32, H b =0.21, 0.19, 0.19 H a -C= 2.54, O-C= 3.47 O- H a =0.96, C-O= 1.41, C- H b = 1.09 BNGR LP* C to LP* B =5.60 O=- 0.50, C= 0.51 C-N= 1.14 C-O= 1.14 BNGR LP N to BD* B-N =0.76 N= 0.20, O= N-N= 2.96 N-O= 1.15 BNGR LP O to BD* C-H =9.44 O=- 0.76, H a =0.49, C=-0.33, H b =0.20, 0.20, 0.22 O-B= 3.00, H a -B= 2.96 O- H a =0.96, C-O= 1.42, C- H b =

3 Table S2. NBO charges on M 3 O + moieties (Q K (M 3 O + )); distance in between the O/M centres of the M 3 O + moieties from the host surface (R + M3O -Surface ) (in Ǻ) in the CO/NO/M 3 O + GR/BGR/BNGR complexes. Systems Q K (M 3 O + ) R + M3O -Surface Q Li =0.78, 0.74, 0.82 Li-C= 2.49 Li 3 O + GR Q O =-1.01 Q Li =0.81, 0.88, 0.78 Li-C= 2.49 Li 3 O + GR Q O =-0.98 Q Li =0.81, 0.80, 0.80 Li-C= 2.57 Li 3 O + GR Q O =-1.52 Q Na =0.81, 0.79, 0.83 Na-C= 2.78 Na 3 O + GR Q O =-1.02 Q Na =0.90, 0.87, 0.90 Na-C= 2.69 Na 3 O + GR Q O =-0.57 Q Na =0.87, 0.86, 0.81 Na-C= 2.85 Na 3 O + GR Q O =-1.58 Q K =0.81, 0.83, 0.82 O-C= 2.96 K 3 O + GR Q O =-0.97 Q K =0.89, 0.92, 0.93 K-C= 2.99 K 3 O + GR Q O =-0.66 Q K =0.85, 0.82, 0.86 K-C= 3.20 K 3 O + GR Q O =-1.53 Q Li =0.90, 0.81, 0.72 O-B= 1.58, Li-C Avg = 2.43 Li 3 O + BGR Q O =-1.23 Q Li =0.89, 0.82, 0.79 O-B= 1.59, Li-C Avg = 2.45 Li 3 O + BGR Q O =-1.26 Q Li =0.89, 0.80, 0.85 O-B= 1.57, Li-C Avg = 2.37 Li 3 O + BGR Q O =-1.23 Q Na =0.91, 0.88, 0.83 O-B= 1.55, Na-C Avg = 2.49 Na 3 O + BGR Q O =-1.58 Q Na =0.93, 0.87, 0.88 O-B= 1.53, Na-C Avg = 2.55 Na 3 O + BGR Q O =-1.25 Q Na =0.91, 0.89, 0.92 O-B= 1.54, Na-C Avg = 2.51 Na 3 O + BGR Q O =-1.23 Q K =0.88, 0.90, 0.91 O-B= 1.52, K-C Avg = 2.81 K 3 O + BGR Q O =-1.16 Q K =0.89, 0.92, 0.92 O-B= 3.84, K-C Avg = 3.00 K 3 O + BGR Q O =-0.56 Q K =0.92, 0.93, 0.90 O-B= 1.51, K-C Avg = 2.80 K 3 O + BGR Q O =-1.18 Li 3 O + BNGR Q Li =0.89, 0.90, 0.70 Q O =-1.29 O-B= 1.54, Li-N Avg = 2.14, Li-C= 2.16 Li 3 O + BNGR Q Li =0.82, 0.89, 0.82 Q O =-1.30 O-B= 1.53, Li-N Avg = 2.12, Li-C= 2.21 Li 3 O + BNGR Q Li =0.82, 0.90, 0.84 Q O =-1.30 O-B= 1.53, Li-N Avg = 2.13, Li-C= 2.29 Na 3 O + BNGR Q Na =0.92, 0.87, 0.83 Q O =-1.27 O-B= 1.48, Na-N Avg = 2.47, Na- C= 2.47 Na 3 O + BNGR Q Na =0.93, 0.88, 0.86 Q O =-1.26 O-B= 1.46, Na-N Avg = 2.52, Na- C= 2.65 Na 3 O + BNGR Q Na =0.93, 0.89, 0.88 Q O =-1.27 O-B= 1.48, Na-N Avg = 2.48, Na- C= 2.55 Q K =0.91, 0.88, 0.90 O-B= 1.45, K-N avg = 2.82, K-C= 3

4 K 3 O + BNGR Q O = K 3 O + BNGR Q K =0.92, 0.92, 0.93 Q O =-0.74 O-B= 1.54, K-N= 2.94, K-C= 2.96 K 3 O + BNGR Q K =0.91, 0.90, 0.94 Q O =-1.23 O-B= 1.44, K-N avg = 2.84, K-C= 2.85 Table S3. Electron density descriptors (in a.u.) at the bond critical points (BCP) for the CO/NO/M 3 O + GR/BGR/BNGR moieties. Herein, subscripts MOL-G, M-G, MOL-M, MOL refer to the BCPs belonging to the adsorbate-gr/bgr/bngr, M 3 O + - GR/BGR/BNGR, adsorbate- M 3 O + and adsorbate moieties respectively. Systems BCP ρ(r c ) 2 (r c ) H(r c ) -G(r c )/V(r c ) ELF GR O-C MOL-G 1.28 C-C MOL-G GR O-C MOL-G 1.23 N-C MOL-G 1.19 N-O MOL GR H-C MOL-G 1.30 O-C MOL-G 1.22 O-H MOL BGR C-C MOL-G 1.37 O-C MOL-G BGR N-C MOL-G O-C MOL-G 1.19 N-O MOL BGR C-C MOL-G

5 H-C MOL-G O-H MOL BNGR C-N MOL-G BNGR N-N MOL-G 1.22 N-O MOL BNGR O-N MOL-G 1.06 C-N MOL-G O-H MOL Li 3 O + GR O-C M-G 1.06 Li-C M-G M O-Li MOL-M Li 3 O + GR O-C M-G 1.06 Li-C M-G 1.30 N-O MOL N-O MOL-M O-Li MOL-M O-C M-G 1.04 Li 3 O + GR Li-C M-G O-H MOL O-Li MOL-M

6 H-C MOL-G 1.19 Na 3 O + GR O-C M-G 1.13 Na-C M-G M O-Na MOL-M Na 3 O + GR O-C M-G 1.16 Na-C M-G N-O MOL N-O MOL-M O-C M-G 1.17 Na 3 O + GR Na-C M-G H-O MOL O-Na MOL-M H-O MOL-M K 3 O + GR O-C M-G 1.14 K-C M-G M O-K MOL-M O-C M-G 1.30 K 3 O + GR K-C M-G N-O MOL N-O MOL-M O-C M-G

7 K 3 O + GR K-C M-G 1.34 H-O MOL-M O-K MOL-M O-H MOL Li 3 O + BGR Li-C M-G C-Li MOL-M C-C MOL-G Li 3 O + BGR Li-C M-G N-O MOL O-Li MOL-M 1.35 N-O MOL-M Li 3 O + BGR Li-C M-G O-H MOL O-Li MOL-M H-C MOL-G Na 3 O + BGR Na-C M-G C-Na MOL-M M

8 C-C MOL-G Na 3 O + BGR Na-C MOL-G N-O MOL O-C MOL-G 1.11 N-C MOL-G N-Na MOL-M Na 3 O + BGR Na-C MOL-G O-H MOL O-Na MOL-M H-C MOL-G K 3 O + BGR K-C M-G M O-K MOL-M 1.38 K-C M-G 1.27 K 3 O + BGR N-O MOL N-O MOL-M O-K MOL-M K 3 O + BGR K-C M-G O-H MOL

9 O-K MOL-M H-O MOL - M Li 3 O + BNGR Li-C M-G C-Li MOL-M C-C MOL-G Li 3 O + BNGR Li-C M-G N-O MOL O-Li MOL-M N-Li MOL-M 1.34 N-O MOL-M Li 3 O + BNGR Li-C M-G O-H MOL O-Li MOL-M H-C MOL-G Na 3 O + BNGR Na-C M-G C-Na MOL-M 1.38 O-Na MOL-M Na 3 O + BNGR Na-C M-G

10 N-O MOL N-C MOL-G O-C MOL-G N-Na MOL-M Na 3 O + BNGR Na-C M-G O-H MOL O-Na MOL-M K 3 O + BNGR K-C M-G C-K MOL-M M K 3 O + BNGR K-C M-G 1.27 N-O MOL O-K MOL-M N-O MOL-M K 3 O + BNGR K-C M-G O-H MOL O-K MOL-M H-C MOL-G 1.22 Figures 10

Figure S1: Geometrical alignment of the adsorbed guest@gr/bgr moieties at 500 fs where (a) Li 3 O

11 Figure S1: Geometrical alignment of the adsorbed moieties at 500 fs where (a) Li 3 O (b) Na 3 O (c) K 3 O (d) Li 3 O and (e) Na 3 O respectively. 11

Figure S2: Geometrical alignment of the adsorbed guest@bgr/bngr moieties at 500 fs where

12 Figure S2: Geometrical alignment of the adsorbed moieties at 500 fs where (a) K 3 O (b) Li 3 O (c) Na 3 O and (d) K 3 O respectively. 12

13 Figure S3. The TDOS plots of (a) GR, (b) BGR and (c) BNGR respectively. 13

14 Figure S4. The TDOS plots of M 3 O where (a) Li 3 O (b) Na 3 O and (c) K 3 O respectively. Here frag1 denotes M 3 O + moieties whereas frag2 denotes GR. The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 14

15 Figure S5. The TDOS plots of M 3 O where (a) Li 3 O (b) Na 3 O and (c) K 3 O respectively. Here frag1 denotes M 3 O + moieties whereas frag2 denotes BGR. The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 15

16 Figure S6. The TDOS plots of M 3 O where (a) Li 3 O (b) Na 3 O and (c) K 3 O respectively. Here frag1 denotes M 3 O + moieties whereas frag2 denotes BNGR. The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 16

17 Figure S7. The TDOS plots of CO/NO/GR where (a) GR, (b) GR and (c) GR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes GR. The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 17

18 Figure S8. The TDOS plots of CO/NO/BGR where (a) BGR, (b) BGR and (c) BGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes BGR. The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 18

19 Figure S9. The TDOS plots of CO/NO/BNGR where (a) BNGR, (b) BNGR and (c) BNGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes BNGR. The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 19

20 Figure S10. The TDOS plots of CO/NO/Li 3 O + GR where (a) Li 3 O + GR, (b) Li 3 O + GR and (c) Li 3 O + GR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes Li 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 20

21 Figure S11. The TDOS plots of CO/NO/Na 3 O + GR where (a) Na 3 O + GR, (b) Na 3 O + GR and (c) Na 3 O + GR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes Na 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 21

22 Figure S12. The TDOS plots of CO/NO/K 3 O + GR where (a) K 3 O + GR, (b) K 3 O + GR and (c) K 3 O + GR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes K 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 22

23 Figure S13. The TDOS plots of CO/NO/Li 3 O + BGR where (a) Li 3 O + BGR, (b) Li 3 O + BGR and (c) Li 3 O + BGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes Li 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 23

24 Figure S14. The TDOS plots of CO/NO/Na 3 O + BGR where (a) Na 3 O + BGR, (b) Na 3 O + BGR and (c) Na 3 O + BGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes Na 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 24

25 Figure S15. The TDOS plots of CO/NO/K 3 O + BGR where (a) K 3 O + BGR, (b) K 3 O + BGR and (c) K 3 O + BGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes K 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 25

26 Figure S16. The TDOS plots of CO/NO/Li 3 O + BNGR where (a) Li 3 O + BNGR, (b) Li 3 O + BNGR and (c) Li 3 O + BNGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes Li 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 26

27 Figure S17. The TDOS plots of CO/NO/Na 3 O + BNGR where (a) Na 3 O + BNGR, (b) Na 3 O + BNGR and (c) Na 3 O + BNGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes Na 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 27

28 Figure S18. The TDOS plots of CO/NO/K 3 O + BNGR where (a) K 3 O + BNGR, (b) K 3 O + BNGR and (c) K 3 O + BNGR respectively. Here frag1 denotes CO/NO/CH 3 OH moieties whereas frag2 denotes K 3 O The vertical line designates the E F whereas the vertical bars represent occupied and virtual orbitals. 28

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