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The Mechanism of Chemisorption of Hydrogen Atom On Graphene Insights From The Reaction Force and Reaction Electronic Flux
The Mechanism of Chemisorption of Hydrogen Atom On Graphene Insights From The Reaction Force and Reaction Electronic Flux
Citation: The Journal of Chemical Physics 141, 134701 (2014); doi: 10.1063/1.4896611
View online: http://dx.doi.org/10.1063/1.4896611
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Quantum study of Eley-Rideal reaction and collision induced desorption of hydrogen atoms on a graphite
surface. I. H-chemisorbed case
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The importance of hydrogen’s potential-energy surface and the strength of the forming R – H bond in surface
hydrogenation reactions
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Dissociative adsorption of NO upon Al(111): Orientation dependent charge transfer and chemisorption reaction
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THE JOURNAL OF CHEMICAL PHYSICS 141, 134701 (2014)
At the PBE-D3/cc-pVDZ level of theory, the hydrogen chemisorption on graphene was analyzed us-
ing the reaction force and reaction electronic flux (REF) theories in combination with electron pop-
ulation analysis. It was found that chemisorption energy barrier is mainly dominated by structural
work (∼73%) associated to the substrate reconstruction whereas the electronic work is the greatest
contribution of the reverse energy barrier (∼67%) in the desorption process. Moreover, REF shows
that hydrogen chemisorption is driven by charge transfer processes through four electronic events tak-
ing place as H approaches the adsorbent surface: (a) intramolecular charge transfer in the adsorbent
surface; (b) surface reconstruction; (c) substrate magnetization and adsorbent carbon atom develops a
sp3 hybridization to form the σ C-H bond; and (d) spontaneous intermolecular charge transfer to reach
the final chemisorbed state. © 2014 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4896611]
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134701-2 Cortés-Arriagada et al. J. Chem. Phys. 141, 134701 (2014)
ξ2 ξP
W3 = − F (ξ )dξ < 0, W4 = − F (ξ )dξ < 0, (3)
ξT S ξ2
FIG. 1. Potential energy (solid line) and reaction force (dashed line) profiles
of an exergonic single step reaction as a function of the reaction coordinate and therefore E◦ and E= of a single step reaction can be
ξ . On top are displayed the boundaries for the reactant (R), transition state expressed as
(TS), and product (P) regions as defined by the minima and critical points in
the energy and reaction force profiles, respectively.
E ◦ = E(ξP ) − E(ξR ) = W1 + W2 + W3 + W4 , (4)
FIG. 2. PAHs used on all calculations. Atomic hydrogen is adsorbed onto C1 . Hydrogen atoms at the edges were deleted in order to simplify.
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FIG. 3. Hydrogen interaction on all graphene models as an adsorption process, depicting reactants (physisorbed state), transition state (TS), and products
(chemisorbed state). Distances are in angstroms (Å).
SCF steps, convergence tolerance values of 1 × 10−6 and 1 interaction with all graphene models as an adsorption process,
× 10−8 hartree were used, respectively. Vibrational frequen- depicting reactants (physisorbed state), transition state (TS),
cies were obtained for stationary points in order to ensure for and products (chemisorbed state). Fig. 4 shows the potential
the nature of reactants, products, and transition states. Atomic energy and reaction force profiles and Table I shows the reac-
net charges, Wiberg bond orders, and hybridization indexes tion and energetic parameters for all analyzed models. Note
were obtained from the Natural Bond Orbital (NBO) Anal- that the process under study is physisorption → chemisorp-
ysis. Basis set superposition errors (BSSE) were corrected tion and the reaction goes from higher to lower values of
by the counterpoise (CP) method by Boys and Bernardi.36 the C1 -H distance. In this context, the works defined through
Structure optimizations were carried-out in the ORCA 3.0.1 Eqs. (2) and (3) change signs.
program,44 and properties calculations were performed in the Firstly, H physisorption take place at ∼3.0 Å on C1 with
Gaussian 09 program.45 an exergonic energy (Ephys ) of −0.68 to −0.80 Kcal/mol,
in agreement with a predicted value of −0.7 Kcal/mol from
DFT calculations using the BP86-D/def2-TZVP method17 ;
IV. RESULTS AND DISCUSSION note that the value from the G4×4 model shows the best
agreement with experimental value of −0.90 Kcal/mol for
A. Potential energy and reaction force profiles
H physisorption on graphite.46 Although both top and hol-
The results consider the adsorption processes as a func- low sites have been theoretically determined to be the mini-
tion of the vertical distance C1 -H1 . Fig. 3 shows the hydrogen mum in the physisorbed state, disposition of H is predicted
FIG. 4. (a) Energy and (b) reaction force profiles in Kcal/mol for hydrogen interaction on all PAHs models. Vertical lines in reaction force account for the
limits among reactants, transitions state, and product regions. W represents the reaction works.
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134701-5 Cortés-Arriagada et al. J. Chem. Phys. 141, 134701 (2014)
=
TABLE I. Physisorption energy (Ephys ), reaction energy (E◦ ), activation energy (E= ), reverse activation energy (Er ), and reaction works (Wn ) according
to reaction force theory. All values include counterpoise and dispersion force correction and are expressed in Kcal/mol.
Ephys = E(PAH − H)phys − (EPAH + EH ); E ◦ = E(P AH −H )chemi − (EP AH + EH ) = Ephys − (W1 + W2 + W3 + W4 ); E = = E(P AH −H )ts
=
− E(P AH −H )phys = −(W1 + W2 ); Er = E(P AH −H )ts − E(P AH −H )chemi = W3 + W4 ; where E(PAH-H)phys , E(PAH-H)chemi , and E(PAH-H)ts are the ener-
gies of the PAH-H system in the physisorbed, chemisorbed and transition state, respectively. EPAH and EH are the energy of the isolated PAH and hydrogen
atom, respectively.
Pyrene −0.68 −13.88 5.25 18.45 −3.78 (72%) −1.47 (28%) 11.68 (63%) 6.77 (37%)
Coronene −0.73 −14.89 5.17 19.33 −3.77 (73%) −1.40 (27%) 12.38 (64%) 6.95 (36%)
G4×4 −0.80 −19.15 4.64 22.99 −3.34 (72%) −1.30 (28%) 15.40 (67%) 7.58 (33%)
Experimental −0.9a −10.3b,c 4.6d 14.0c,e −3.3f −1.3f 9.4f 4.6f
a
Experimental values were obtained from Ref. 46.
b
Estimated from Refs. 20, 46, and 47.
c
Note that inclusion of ZPE corrections affects energy parameters in ∼4 Kcal/mol when chemisorbed state is involved.
d
Experimental values were obtained from Ref. 20.
e
Experimental values were obtained from Ref. 47.
f
Estimated from percentage associated to reaction works of the H-G4×4 system.
to be in the top site on C1 atom, which is even a discus- activation energy of H bonded on graphite (∼14 Kcal/mol).47
sion focus from DFT and ab initio calculations.10, 15–17 In It is important to note that inclusion of ZPE corrections
the next stage, H chemisorption on top site of all adsorbents (Table S1 in the supplementary material)52 affects energy pa-
leads to exergonic products over-passing a chemisorption bar- rameters in ∼4 Kcal/mol when chemisorbed state is involved,
rier that ranges from 5.25 to 4.64 Kcal/mol, depending on in agreement with thermochemical calculations, which is
the adsorbent and in good agreement with the experimental due to strong H bonding to the surface in the chemisorbed
value of ∼4.6 Kcal/mol.20 The smallest barrier is obtained state.17
with the G4×4 model, indicating the importance of disper- Reaction force allows fragmenting the reaction coordi-
sion forces in an extended surface to allow the chemisorp- nate in three regions (reactants, transition state and products)
tion on graphitic surfaces from the physisorbed state. Be- according to critical points located at ξ ≈ 2.0 and ξ ≈ 1.3 Å
sides, this barrier is high enough to prevent chemisorption in the reaction force profile (Fig. 4(b)). By using Eqs. (2) and
at ambient conditions.14 Transition state is located at a C1 - (3), the reaction works involved at each region along the reac-
H1 distance of ∼1.8 Å, which agree with distances deter- tion coordinate are obtained. From W1 and W2 , the works in-
mined theoretically (1.72–1.80 Å)10, 12, 15–17 ; at this point, C1 volved in the chemisorption energy barrier (E= ) were found,
atom is placed over the plane of the PAH due to the hy- which would be mainly dominated by structural rearrange-
bridization change from sp2 to sp3 to form a σ bond between ments in a 72%–73%. The magnitude of W1 is well related to
1s (H1 ) and 2pz (C1 ) orbitals in the chemisorbed state. Fi- the substrate reconstruction needed to allow the chemisorp-
nally, chemisorption is reached at ∼1.13 Å in the reaction co- tion occurring above the TS distance (ξ > 1.8 Å),8 indicating
ordinate, with exergonic chemisorption energies of −13.88, that reconstruction of the host material is the main effect in-
−14.89 and −19.15 kcal/mol for pyrene, coronene and G4×4 , volved in the adsorption barrier, which has been shown to be
respectively, in agreement with values reported for related needed to allow the chemisorption of hydrogen.8, 21 Assum-
models.5, 8, 10, 12–19, 48 A deeper minimum is found for the G4×4 ing the same relative weight of W1 and W2 to define E= in
model in ∼5 Kcal/mol compared to pyrene and coronene, the H-G4×4 system, the experimental value of reaction works
indicating the importance of lattice size to determine accu- can be estimated, they are also displayed in Table I. Until TS,
rate values of E◦ to compare with graphite or graphene. In- adsorption is mainly dominated by dispersion forces, there-
deed, G4×4 chemisorption energy is very close to values de- fore the work associated to electronic effects is lesser than
termined from extended models as C42 H16 (−19.14 Kcal/mol, the structural one, with contributions of 27%–28%. After TS,
B3LYP/6-31G(d,p)12 and graphene under periodic bound- chemisorption is mainly driven by spontaneous electronic re-
ary conditions avoiding BSSE (∼−19 Kcal/mol; PBE/plane arrangements, with W3 of 64%–67% of the reverse energy
=
waves).14, 48 Moreover, although three different sites are com- barrier (Er ). Finally, W4 shows structural rearrangements
=
monly proposed for adsorption of atoms on graphene (top, ad- corresponding to the 33%–36% of Er , respectively; 3%
sorption on carbon atom; bridge, adsorption on C-C bonding; lesser of G4×4 than coronene and pyrene would be due to
and hollow, adsorption at the centre of benzene type ring),12, 16 the fact that the later ones are distorted at the edges near to
theoretical studies show that the adsorption of atoms with one C1 . Note that W4 and W3 are negatives for the chemisorp-
valence electron take place on the top site,49 therefore our re- tion process; therefore positive values of W4 and W3 repre-
sults agree with these findings. sent the most important works involved in the endergonic H
The reverse energy barrier characterizes the desorption desorption. In summary, reaction force indicates that for the
process, which needs over-passing a barrier larger than 18 chemisorption process, the structural work is the most impor-
Kcal/mol, naturally due to that desorption is a bond breaking tant contribution to the energy barrier (W1 > W2 ), while that
=
process; corrected Er by zero point energy (ZPE) have in the desorption process, electronic work is the greatest con-
reasonable agreement with the experimental desorption tribution (W3 > W4 ).
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134701-6 Cortés-Arriagada et al. J. Chem. Phys. 141, 134701 (2014)
FIG. 6. (a) Reaction Electronic Flux (REF, J(ξ )) profiles in Kcal/mol Å, for hydrogen adsorption on all adsorbents. (b) Decomposed J(ξ ) profile in transfer (Jt )
and polarization (Jp ) contributions for the H-G4×4 model.
to the TS region, which is due to charge decrease of C1 atom produce reliable REF profiles of the system. In addition, REF
and not H1 or the surrounding C atoms, as noted from charge indicates that most of the electronic events are occurring in
profile in Fig. 7. This step in the reaction is allowing the sub- the TS region, as indicated by the reaction force, and support-
strate reconstruction and sp3 hybridization of C1 in a later ing W2 and W3 are mainly electronic works even if structural
step. The two peaks in the Jt (ξ ) into the TS region indicate changes are also taking place in the TS region.
two spontaneous charge transfer events [Jt (ξ ) > 0]. The first
one at the TS distance (∼1.80 Å), mainly associated with the
intramolecular electronic reordering due to the surface recon- C. Bond orders and C1 atom hybridization
struction and formation of the TS because of the charge trans- Fig. 8 shows the Wiberg bond order derivatives and hy-
fer from hydrogen is <0.04 electrons at this point. The second bridization of C1 atom along the reaction coordinate for the
event with Jt (ξ ) > 0 is in the limit of TS-P regions (∼1.34 Å) G4×4 system. The highest intensity of bond order reordering
coming from the final electronic reordering before to reach takes place in the TS region (∼1.6 Å); note that weakening
the chemisorbed state including charge transfer from the ad- (negative derivative) and strengthening (positive derivative)
sorbed H atom (∼0.3 electrons). From the dipole moment, we of C1 -CN (parameter associated to the surface reconstruction)
found local minima at 1.34 Å (0.1 D) and a peak at ∼1.80 Å and C1 -H1 bonds, respectively, are occurring at the same time,
(0.6 D) indicating important charge density distributions at i.e., the process is synchronous. Moreover, from the C1 hy-
these points in agreement with the peaks in Jt (ξ ), which are bridization profile, we can see the snappish change of sp2
qualitatively related with intensity in the changes of dipole to sp3 occurs at ∼1.6 Å, after the TS, the same point where
moment. the bond order derivative reaches its maximum value. These
Finally, a poorly defined maximum of pyrene is noted in changes along the reaction coordinate match with the minima
the TS region of J(ξ ) profile, most possibly due to the sys- of J(ξ ) and Jt (ξ ) profiles in the TS region at ∼1.6 Å. This
tem size since coronene and G4×4 exhibit a quite similar REF result indicates that at this point occurs the forming of C1 -
profile; so we recommend using at least coronene in order to H1 bond, and C1 develops a sp3 hybridization, just after the
FIG. 7. Charge of H1 and CN (N = 1, 2, 3, and 4) atoms and total dipole FIG. 8. Wiberg bond order derivative of C1 -H1 and C1 -CN (N = 2, 3, and
moment in debye (D) along the reaction coordinate for the H-G4×4 system. 4) bonds and hybridization of C1 atom along the reaction coordinate for the
All systems are included in the supplementary material.52 H-G4×4 system. All systems are included in the supplementary material.52
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134701-8 Cortés-Arriagada et al. J. Chem. Phys. 141, 134701 (2014)
V. CONCLUSIONS
At the PB3-D3/cc-pVDZ level of theory, the steps in-
volved in the chemisorption of hydrogen onto graphene were
fully analyzed from the reaction force and reaction electronic
flux. As models of graphene we used pyrene, coronene and a
G4×4 cell. Our results indicate that the minimum size model
to study the adsorption of hydrogen onto graphene can be rep-
resented by coronene. However, an extended surface as G4×4
model is necessary to determine accurate values of adsorption
energies and comparing with graphitic surfaces.
Reaction energies and barriers were in good agreement
with experimental data. Through the reaction force analysis,
it was determined that chemisorption energy barrier is mainly
FIG. 9. Natural bond orbitals (NBOs) describing the σ bond at the dominated by structural work (73%) associated to the sub-
chemisorbed state. No NBO is found for the C1 -H1 bond at the TS distance, strate reconstruction, while the electronic work is the great-
only natural atomic orbitals (NAOs) corresponding to 2pz of C1 atom and 1s est contribution (67%) to desorption activation energy. On
of H1 atom.
the other hand, reaction electronic flux in combination with
the NBO electron population analysis shows that four steps
transition state. Indeed, Fig. 9 shows that there is no NBO are involved in all chemisorption process: (a) intramolecular
associated with the C1 -H1 bond in the TS. After this point, charge redistribution in the adsorbent; (b) surface reconstruc-
adsorption (or desorption) can go forward by spontaneous tion and spontaneous charge density distribution; (c) change
charge transfer processes as discussed above. In addition, in hybridization of C1 to allow formation of the C1 -H1 bond,
this information from the REF profile indicates that in the and substrate magnetization (midgap state of graphene) in-
chemisorption process, graphene loses aromaticity after the duced by unpaired electron on the adsorbent surface; and
TS is established, indicating that TS is similar to the reactants. (d) final spontaneous intermolecular charge redistribution to
Finally, from Fig. 10, it is interesting to note that the reach the final chemisorbed state. Note that electronic activ-
high intensity in the spin density change takes place at the ity taking place in steps (c) and (d) explains why the des-
same point discussed above, suggesting the midgap state of orption energy barrier is mainly dominated by electronic ef-
graphene or the substrate magnetization, induced by pz va- fects. In this way, reaction force and REF show to be useful
cancy unpaired electron on the adsorbent surface,22 is cre- tools to study the processes whereby adsorbates interact onto
ated simultaneously with the bond weakening/strengthening surfaces.
and where the C1 hybridization change reaches the maxi-
mum intensity, as indicated by REF at ξ ≈ 1.6 Å. These
last findings allow establish the main process involved in ACKNOWLEDGMENTS
the reverse activation energy, which was found to be dom-
inated by electronic effects. Note that in the desorption The authors thank FONDECYT through Project Nos.
process, the events taking place are opposite to those dis- 1130072, 1120093, and 1141098 and ICM Grant No. 120082
cussed, i.e., change in the spin state of the adsorbent for financial support. D.C.-A. acknowledges Postdoctoral
from high to low spin, charge transfer to reach the tran- FONDECYT Project No. 3140314 and to QTC members R.
sition state, and change in hybridization of C1 from sp3 Duran, S. Miranda, D. Ortega, and N. Villegas for useful
to sp2 . discussions.
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