The mechanism of chemisorption of hydrogen atom on graphene: Insights from the

reaction force and reaction electronic flux

Diego Cortés-Arriagada, Soledad Gutiérrez-Oliva, Bárbara Herrera, Karla Soto, and Alejandro Toro-Labbé

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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 THE JOURNAL OF CHEMICAL PHYSICS 141, 134701 (2014)

The mechanism of chemisorption of hydrogen atom on graphene:

Insights from the reaction force and reaction electronic flux
Diego Cortés-Arriagada,a) Soledad Gutiérrez-Oliva, Bárbara Herrera, Karla Soto,
and Alejandro Toro-Labbé
Nucleus Millennium Chemical Processes and Catalysis, Laboratorio de Química Teórica Computacional
(QTC), Departamento de Química-Física, Facultad de Química, Pontificia Universidad Católica de Chile, Av.
Vicuña Mackenna 4860, Macul, Santiago, Chile
(Received 19 June 2014; accepted 16 September 2014; published online 1 October 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]

I. INTRODUCTION ∼1.7–1.8 Å. In the chemisorbed state, hydrogen atom bonds

The adsorption of atoms and molecular system on sur-
faces is today a broad field of study mainly in the effort to
understand the processes whereby adsorbates interacts on the
adsorbents, chemical modification of surfaces allowing ad-
sorption of new analites, or mechanism whereby adsorbates
form new molecules. In this sense, a considerable amount of
experimental and theoretical studies has been developed to
analyze the interaction of hydrogen (and hydrogen molecule)
onto graphitic surfaces. The aim is mainly from its implica-
tions in use for hydrogen storage,1, 2 study of hydrogen-wall
interactions in reactors for nuclear fusion technology,3–5 band
gap tuning for nanoscale electronic devices,6, 7 and to clar-
ify the formation of hydrogen molecule in the interstellar me-
dia proposed to take place by recombination on graphitic dust
grains.8–11
As noted above, several theoretical studies have been
developed to characterize the interaction of hydrogen onto
graphitic surfaces employing polycyclic aromatic hydrocar-
bons (PAHs) (as coronene or pyrene) and periodic surfaces
of graphite or graphene.5, 8, 10, 12–19 Mainly, a lot of den-
sity functional theory (DFT) methods were employed in
order to account for accurate values of energetic parame-
ters, which has shown to be in good agreement with rigor-
ous coupled cluster methods like CCSD(T)/cc-pVTZ.15 From
these studies, it was predicted that H physisorption onto
graphitic surfaces takes place at ∼3.0 Å onto the surface.
For chemisorption, the hydrogen atom need to overcome a
predicted barrier of ∼4.6 Kcal/mol, confirmed from experi-
ments by high-resolution electron energy loss spectroscopy,20
forming a transition state onto a C atom (so-called top site) at
a) Author to whom correspondence should be addressed. Electronic mail:
dcortesr@uc.cl
to C atom and in the process the latter develops sp3 hybridiza-
tion and puckers out of the surface basal plane; therefore, the
substrate reconstruction is necessary to allow the hydrogen
atom chemisorption on graphene.8, 21 All process has been
predicted with a reaction energy of ∼12.5 Kcal/mol15 and
generates on graphene the midgap state due to a pz unpaired
electron.22 All of these analyses have focused into study only
the stationary points on the potential energy surface, being
necessary an extended analysis along the reaction coordinate
to gain insights about the overall processes taking place dur-
ing the adsorption.
Expecting the adsorption on graphene involves processes
such as charge transfer, bond weakening, and bond strength-
ening, we can characterize them from chemical descriptors
as those proposed from the DFT. In recent years, reaction
force23 and reaction electronic flux24, 25 has been used to
rationalise mechanisms involved in a wide type of chemi-
cal reactions as SN 2, proton transfers, isomerisations, among
others.26–28 However, its use in adsorption problems involv-
ing physical and chemical interactions has not been explored
yet. In this work, by employing a dispersion corrected DFT
method, we use the reaction force and reaction electronic flux
to study the mechanism whereby hydrogen is chemisorbed
onto graphitic surfaces. In addition, to account for the relia-
bility of the chemical information obtained by these descrip-
tors, we compared it to that coming from electron population
analysis.
II. THEORY
A. Reaction force
In the course of a chemical or physical process, the force
F is defined as the negative of the energy derivative along the

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 134701-2 Cortés-Arriagada et al.
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
ξ . On top are displayed the boundaries for the reactant (R), transition state
(TS), and product (P) regions as defined by the minima and critical points in
the energy and reaction force profiles, respectively.
reaction coordinate ξ :23
dE
F (ξ ) = − . (1)
dξ
F(ξ ) is refereed as the reaction force; this global property is
zero at every maximum or minimum of the potential energy
profile (E(ξ )) and presents critical points where the derivative
of the E(ξ ) is zero. In a single step reaction R → P, where re-
actants (R) converts into products (P) passing through a tran-
sition state (TS), two critical points are found: at ξ 1 between
ξ R and ξ TS and at ξ 2 between ξ TS and ξ P (Fig. 1). By means of
ξ 1 and ξ 2 it is possible to define the reaction regions in which
different phenomena might be taking place; these are the re-
actant [ξ R , ξ 1 ], transition state [ξ 1 , ξ 2 ], and product [ξ 2 , ξ R ]
regions. The physical interpretation of F(ξ ) emerges through
the analysis of the mechanism that might be driving the reac-
tion at every reaction region. At the reactant region, in the [ξ R ,
ξ 1 ] range there is a retarding force reaching a maximum value
at ξ 1 . In the transition state region [ξ 1 , ξ 2 ], appears a driving
force balancing the retarding force and reaching a maximum
at ξ 2 , passing by the TS where retarding and driving forces
are cancelled at ξ TS . In the final step, between [ξ 2 , ξ R ], the
driving force decreases as the products are obtained.
Studies of many kinds of chemical reactions26–32 have
shown the main effects dominating in each region. Reactant
region is preparative in nature and structural effects associated
with geometrical changes in the chemical species (i.e., bond
stretching, angle bending, geometrical changes due to atomic
re-hybridization, etc.) prevail, in agreement with the retard-
ing character of the F(ξ ) in this region. In the transition state
region, the driving force is mainly associated with electronic
reordering (coming from bond formation/strengthening, bond
break/weakening, charge transfer, polarization, etc.). Most of
the electronic activity that occurs in a chemical reaction takes
place in the transition state region. Finally, in the product re-
gion, structural relaxation takes over and drives the reaction
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J. Chem. Phys. 141, 134701 (2014)
until reaching the final state. In summary, although structural
and electronic effects are present all along the process R →
P, it has been shown that structural effects are dominant in the
reactant and products regions whereas changes in electronic
properties dominate within the transition state region.
Integration of F(ξ ) within the reaction regions allows ob-
taining a decomposition of the reaction (E◦ ) and activation
(E= ) energies. In the case of a single step reaction, one can
define:
ξ1 ξT S
W1 = − F (ξ )dξ > 0, W2 = − F (ξ )dξ > 0, (2)
ξR ξ1
ξ2 ξP
W3 = − F (ξ )dξ < 0, W4 = − F (ξ )dξ < 0, (3)
ξT S ξ2
and therefore E◦ and E= of a single step reaction can be
expressed as
 
E ◦ = E(ξP ) − E(ξR ) = W1 + W2 + W3 + W4 , (4)
 
E = = E(ξT S ) − E(ξR ) = W1 + W2 . (5)
From Eqs. (4) and (5) it is possible to analyze the pre-
dominant effects on E◦ and E= from the relative weight of
the involved reaction works and character of each region. In
this context, W1 and W4 are mainly structural energies while
W2 and W3 are mainly associated to electronic processes. For
instance, the energies required for the structural changes in
reactant region (W1 ) plus energy mainly associated to elec-
tronic reordering in the first stage in the TS region (W2 ) define
the activation energy, and the activation energy appears to be
defined through a balance between structural and electronic
effects. In this context the nature of the activation energy can
be characterized through the relative contribution of W1 and
W2 to E= .
B. Reaction electronic flux
Conceptual DFT provides a set of properties that charac-
terize both global and local reactivity of molecules, they are
obtained from the derivatives of the energy E with respect to
the number of electrons N and the external potential υ(r).33 At
the global level, the electronic chemical potential character-
izes the response of E with respect to changes in N, at constant
υ(r). Chemical potential (μ) is related to the electronegativity
χ thought μ = −χ .34
 
∂E ∼
μ= = −χ . (6)
∂N υ(r)
Use of the finite difference approximation allows to ob-
tain the chemical potential in terms of the first ionization po-
tential (IP) and the electron affinity (EA). Further approxima-
tion using the Koopmans Theorem leads to μ in terms of the
 134701-3 Cortés-Arriagada et al. J. Chem. Phys. 141, 134701 (2014)

eigenvalues ε of the frontier orbitals [HOMO (H) and LUMO i=n 


Ni d  
i=n
(L)]: Jt (ξ ) = Jti (ξ ) = μi (ξ ) − μ(ξ ) , (12)
N dξ
  i=1 i=1
∂E 1 1
μ= ≈ − (I P + EA) ≈ (εH + εL ). (7) where Ni and N are the number of electrons at fragment i and
∂N υ(r) 2 2
in the whole system, respectively; μi stands for the chemi-
cal potential of fragment i. The condensed polarization flux
Note that Eq. (7) is only applicable for closed-shell sys- Jpi (ξ ) is related to the electron density deformation of frag-
tems. For the open-shell case we need to use a general form ment i caused by external field of the other fragments; Jti (ξ )
as defined from the spin polarized DFT:35 accounts for inter-fragments electron transfer processes. In
 β β
 order to obtain μi , frontier orbital eigenvalues of the frag-
∼ 1 εH α
+ εH εLα + εL ment i with the basis set of the whole system are used, as
μ= + , (8)
2 2 2 obtained by the counterpoise method.36 An extended revision
of REF and reaction force theories can be found in the original
where α and β stand for the spin state. In the closed-shell case works.23–25
β β
εHα
= εH and εLα = εL , therefore Eq. (8) is reduced to Eq. (7).
In this context, profiles of chemical potential along a reac-
tion coordinate might be obtained quite easier. The reaction III. COMPUTATIONAL DETAILS
electronic flux determines the changes of μ along the reaction For all simulations, and in order to account for a model
coordinate ξ :24, 25 that allows an adequate description of reaction force and re-
dμ action electronic flux profiles, we adopted three types of poly-
J (ξ ) = − . (9) cyclic aromatic hydrocarbons (PAHs) as finite models for
dξ
graphene (Fig. 2): pyrene (C16 H10 ), coronene (C24 H12 ), and
a zigzag model called G4×4 (C48 H18 ). At the DFT level, the
It has been shown that J(ξ ) is related with the spon- PBE37 functional was used in combination with the Dun-
taneity of the electronic activity taken place along the reac- ning correlation consistent polarized double zeta basis set
tion coordinate. In this sense, positive values of REF indicate (cc-pVDZ). PBE functional was selected considering its per-
spontaneous changes in the electronic density driven by bond formance on non-covalent interactions of adsorbates upon
strengthening or bond formation processes; while, negative graphene in reported and our previous works.38, 39 The spin
values of REF indicate that non-spontaneous changes of the unrestricted formalism (UPBE) was used for calculations
electron density driven by bond weakening or breaking pro- involving open-shell electronic states. In these cases, mix-
cesses. In addition, although charge transfer and polarization ture of higher spin states was found to be negligible; the
are phenomena difficult to separate during a physical or chem- maximum obtained value for the spin-squared operator S(S
ical process, a partition has been proposed25 in the context of + 1)(where S is the spin angular momentum) was 0.76 in
REF theory as follows: comparison to an expected value of 0.75, discarding spin
contamination problems during calculations (Fig. S1 in the
J (ξ ) = Jp (ξ ) + Jt (ξ ), (10) supplementary material).52 Dispersion force effects for en-
ergy and gradients were included by the pairwise dispersion
where [Jp (ξ )] and [Jt (ξ )] stand for polarization and transfer
correction DFT-D3, in combination with the Becke-Johnson
contributions. A partition of the molecular system in i molec-
damping scheme in order to avoid repulsive interatomic forces
ular fragments allows obtaining Jp (ξ ) and Jt (ξ ) by fragment
at short distances.40–42 Relaxed potential energy surface (PES)
contributions:25
scans were performed along of the reaction coordinate C1 -

i=n i=n 
 H1 , obtaining 60 points from 1.0 to 3.5 Å. In geometry opti-
Ni dμi
Jp (ξ ) = Jpi (ξ ) =− , (11) mizations, the Broyden–Fletcher–Goldfarb–Shanno Hessian
N dξ
i=1 i=1 update method43 was adopted. In geometry optimization and

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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 134701-4 Cortés-Arriagada et al. J. Chem. Phys. 141, 134701 (2014)

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
× 10−8 hartree were used, respectively. Vibrational frequen-
cies were obtained for stationary points in order to ensure for
the nature of reactants, products, and transition states. Atomic
net charges, Wiberg bond orders, and hybridization indexes
were obtained from the Natural Bond Orbital (NBO) Anal-
ysis. Basis set superposition errors (BSSE) were corrected
by the counterpoise (CP) method by Boys and Bernardi.36
Structure optimizations were carried-out in the ORCA 3.0.1
program,44 and properties calculations were performed in the
Gaussian 09 program.45
IV. RESULTS AND DISCUSSION
A. Potential energy and reaction force profiles
The results consider the adsorption processes as a func-
tion of the vertical distance C1 -H1 . Fig. 3 shows the hydrogen
interaction with all graphene models as an adsorption process,
depicting reactants (physisorbed state), transition state (TS),
and products (chemisorbed state). Fig. 4 shows the potential
energy and reaction force profiles and Table I shows the reac-
tion and energetic parameters for all analyzed models. Note
that the process under study is physisorption → chemisorp-
tion and the reaction goes from higher to lower values of
the C1 -H distance. In this context, the works defined through
Eqs. (2) and (3) change signs.
Firstly, H physisorption take place at ∼3.0 Å on C1 with
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 ;
note that the value from the G4×4 model shows the best
agreement with experimental value of −0.90 Kcal/mol for
H physisorption on graphite.46 Although both top and hol-
low sites have been theoretically determined to be the mini-
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.

Adsorbent Ephys E◦ E= E= r W1 W2 W3 W4

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-
sion focus from DFT and ab initio calculations.10, 15–17 In
the next stage, H chemisorption on top site of all adsorbents
leads to exergonic products over-passing a chemisorption bar-
rier that ranges from 5.25 to 4.64 Kcal/mol, depending on
the adsorbent and in good agreement with the experimental
value of ∼4.6 Kcal/mol.20 The smallest barrier is obtained
with the G4×4 model, indicating the importance of disper-
sion forces in an extended surface to allow the chemisorp-
tion on graphitic surfaces from the physisorbed state. Be-
sides, this barrier is high enough to prevent chemisorption
at ambient conditions.14 Transition state is located at a C1 -
H1 distance of ∼1.8 Å, which agree with distances deter-
mined theoretically (1.72–1.80 Å)10, 12, 15–17 ; at this point, C1
atom is placed over the plane of the PAH due to the hy-
bridization change from sp2 to sp3 to form a σ bond between
1s (H1 ) and 2pz (C1 ) orbitals in the chemisorbed state. Fi-
nally, chemisorption is reached at ∼1.13 Å in the reaction co-
ordinate, with exergonic chemisorption energies of −13.88,
−14.89 and −19.15 kcal/mol for pyrene, coronene and G4×4 ,
respectively, in agreement with values reported for related
models.5, 8, 10, 12–19, 48 A deeper minimum is found for the G4×4
model in ∼5 Kcal/mol compared to pyrene and coronene,
indicating the importance of lattice size to determine accu-
rate values of E◦ to compare with graphite or graphene. In-
deed, G4×4 chemisorption energy is very close to values de-
termined from extended models as C42 H16 (−19.14 Kcal/mol,
B3LYP/6-31G(d,p)12 and graphene under periodic bound-
ary conditions avoiding BSSE (∼−19 Kcal/mol; PBE/plane
waves).14, 48 Moreover, although three different sites are com-
monly proposed for adsorption of atoms on graphene (top, ad-
sorption on carbon atom; bridge, adsorption on C-C bonding;
and hollow, adsorption at the centre of benzene type ring),12, 16
theoretical studies show that the adsorption of atoms with one
valence electron take place on the top site,49 therefore our re-
sults agree with these findings.
The reverse energy barrier characterizes the desorption
process, which needs over-passing a barrier larger than 18
Kcal/mol, naturally due to that desorption is a bond breaking
=
process; corrected Er by zero point energy (ZPE) have
reasonable agreement with the experimental desorption
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activation energy of H bonded on graphite (∼14 Kcal/mol).47
It is important to note that inclusion of ZPE corrections
(Table S1 in the supplementary material)52 affects energy pa-
rameters in ∼4 Kcal/mol when chemisorbed state is involved,
in agreement with thermochemical calculations, which is
due to strong H bonding to the surface in the chemisorbed
state.17
Reaction force allows fragmenting the reaction coordi-
nate in three regions (reactants, transition state and products)
according to critical points located at ξ ≈ 2.0 and ξ ≈ 1.3 Å
in the reaction force profile (Fig. 4(b)). By using Eqs. (2) and
(3), the reaction works involved at each region along the reac-
tion coordinate are obtained. From W1 and W2 , the works in-
volved in the chemisorption energy barrier (E= ) were found,
which would be mainly dominated by structural rearrange-
ments in a 72%–73%. The magnitude of W1 is well related to
the substrate reconstruction needed to allow the chemisorp-
tion occurring above the TS distance (ξ > 1.8 Å),8 indicating
that reconstruction of the host material is the main effect in-
volved in the adsorption barrier, which has been shown to be
needed to allow the chemisorption of hydrogen.8, 21 Assum-
ing the same relative weight of W1 and W2 to define E= in
the H-G4×4 system, the experimental value of reaction works
can be estimated, they are also displayed in Table I. Until TS,
adsorption is mainly dominated by dispersion forces, there-
fore the work associated to electronic effects is lesser than
the structural one, with contributions of 27%–28%. After TS,
chemisorption is mainly driven by spontaneous electronic re-
arrangements, with W3 of 64%–67% of the reverse energy
=
barrier (Er ). Finally, W4 shows structural rearrangements
=
corresponding to the 33%–36% of Er , respectively; 3%
lesser of G4×4 than coronene and pyrene would be due to
the fact that the later ones are distorted at the edges near to
C1 . Note that W4 and W3 are negatives for the chemisorp-
tion process; therefore positive values of W4 and W3 repre-
sent the most important works involved in the endergonic H
desorption. In summary, reaction force indicates that for the
chemisorption process, the structural work is the most impor-
tant contribution to the energy barrier (W1 > W2 ), while that
in the desorption process, electronic work is the greatest con-
tribution (W3 > W4 ).
 134701-6 Cortés-Arriagada et al.
FIG. 5. Evolution along the reaction coordinate for C1 -CN (N = 2, 3, and 4)
distance and C2 -C1 -C3 -C5 dihedral angle. Atom labels are depicted in Fig. 2.
Results for G4×4 are presented as representative for all adsorbents (all results
included in the supplementary material).52
In order to account for the structural nature of W1 and
W4 , we analyze the structural changes along the reaction co-
ordinate associated to the substrate reconstruction (Fig. 5). In
addition to C1 -H1 distance, we account for C1 -CN distance,
where N is the label for adjacent atoms to C1 (Fig. 2). It can
be seen C1 -CN distance starts at 1.42–1.43 Å, according to
C-C bond in graphene. From reactants to the first region of
TS, C1 -CN distance changes ∼0.02 Å, according with the low
barrier for chemisorption. Furthermore, when TS is reached,
C1 -CN distance increase dramatically until chemisorbed state
is reached; at this point on the surface is found a C1 -CN bond
of ∼1.52 Å, near to the value of a diamond type structure. Be-
sides, the dihedral angle C2 -C1 -C3 -C5 measures as C1 atom
puckers out of the basal plane changing the surface planarity;
this structural change is involved in E= because it starts to
decrease at ξ ≈ 2.5Å from 180◦ to ∼160◦ in the chemisorp-
tion region where C1 develops sp3 hybridization. The results
indicate that both W2 and W3 involve structural components,
but electronic effects in TS region will be dominant as dis-
cussed below by means of the REF analysis. The above dis-
cussion points out that most of the structural effects in W1 are
due to reconstruction at the graphene surface.
According to the surface reconstruction that dominates
the energy barrier of H chemisorption on the graphene mod-
els, it could be expected that this barrier will be affected
by the doping level. The activation energy is expected to be
reduced through controlling the substrate reconstruction be-
fore adsorption. This can be done by doping the surface with
dopants atoms with larger atomic radii compared to a car-
bon atom, which avoid surface reconstruction due to doping
process is itself highly structural and changes the local struc-
ture of the surface. For instance, the energy profiles of H ad-
sorbed on A-doped G4×4 model (where A is Al, Si, or P) show
that the adsorption proceeds without an activation energy bar-
rier associated. In this regard, Fukushima et al. report a de-
crease of ∼3 Kcal/mol in the activation energy of H adsorp-
tion on Al-doped graphene50 with respect to the undoped sur-
face. On the other hand, doping with atoms of similar radii
compared to carbon, as nitrogen or boron, does not affect
the topological structure of the graphitic surface, so that the
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J. Chem. Phys. 141, 134701 (2014)
surface must develops reconstruction to allow the chemisorp-
tion resulting in an activation energy barrier. In fact, in the
case of N-doped G4×4 , we estimate activation energy barrier
> 10 Kcal/mol. Furthermore, the decrease of the activation
barrier would result in an increase of the binding energy.32
In other respects, Huang et al.51 establish that an increase in
the desorption energy barrier is reached by charge doping,
which decrease the energy cost necessary to break the aro-
matic π bonds in graphene and enhancing the strength of the
C-H bond in the chemisorbed state. From the chemical point
view, the transition state would be more difficult to reach.
As shown above, desorption energy barrier is dominated by
electronic work, hence for H desorption from a charge doped
substrate, it is expected that electronic effects associated with
bond break/weakening are increased as the transition state re-
gion is increased. Taking into account hole and electron dop-
ing in the H-G4×4 system, it was found that W3 increase from
67% (in the undoped substrate) to 80% (in both charge-doped
substrates).
B. Reaction electronic flux
Fig. 6(a) depicts the J(ξ ) profiles for H adsorption on all
the adsorbents and shows four critical points with the elec-
tronic events occurring during the chemisorption. In the re-
actant region we observe a slightly J(ξ ) < 0 indicating a
non-spontaneous electronic activity associated with the bond
weakening of C1 -CN bonds; intensity of REF in this region
is low due to structural rearrangements and dispersion forces
dominate the chemisorption barrier as indicated by the reac-
tion force. Entering to the TS region, two maxima (J(ξ ) > 0)
are found: the first one in the TS distance indicating the C1 -
H1 bond strengthening, and the second one entering into the
product region that can be associated to the final electronic
arrangement on all the system to reach the final chemisorbed
state.
It is necessary to point out that from REF theory it can
be expected that most of the electronic activity be associated
to charge transfer contributions. The polarization effect of H
atom on the adsorbent electron density is minimal due to its
reduced electron density compared to the adsorbent. Indeed,
polarization flux has a minimal activity along the reaction co-
ordinate as shown in Fig. 6(b); therefore, the chemisorption
process is dominated by charge transfer effects. On the other
hand, according to Eqs. (11) and (12), as N  NH on these
systems (ZH = 1), both polarization and transfer effects are
dominated by the adsorbent (decomposition by fragment is
not necessary). Taking this into account, we can characterize
the four electronic events mentioned above by analyzing other
independent electronic properties such as atomic charges,
bond orders and hybridization degree of the adsorbent car-
bon atom (Fig. 7). These properties were selected for the
G4×4 model as representative for all the adsorbents (all sys-
tems are included as the supplemental material).52 From the
zero flux regime, chemisorption begins with non-spontaneous
[Jt (ξ ) < 0] intramolecular charge transfer from the C1 atom
to the adsorbent thus weakening the C1 -CN bonds. This fact
is in agreement to increase in the total dipole moment near
 134701-7 Cortés-Arriagada et al.
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
and not H1 or the surrounding C atoms, as noted from charge
profile in Fig. 7. This step in the reaction is allowing the sub-
strate reconstruction and sp3 hybridization of C1 in a later
step. The two peaks in the Jt (ξ ) into the TS region indicate
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-
struction and formation of the TS because of the charge trans-
fer from hydrogen is <0.04 electrons at this point. The second
event with Jt (ξ ) > 0 is in the limit of TS-P regions (∼1.34 Å)
coming from the final electronic reordering before to reach
the chemisorbed state including charge transfer from the ad-
sorbed H atom (∼0.3 electrons). From the dipole moment, we
found local minima at 1.34 Å (0.1 D) and a peak at ∼1.80 Å
(0.6 D) indicating important charge density distributions at
these points in agreement with the peaks in Jt (ξ ), which are
qualitatively related with intensity in the changes of dipole
moment.
Finally, a poorly defined maximum of pyrene is noted in
the TS region of J(ξ ) profile, most possibly due to the sys-
tem size since coronene and G4×4 exhibit a quite similar REF
profile; so we recommend using at least coronene in order to
FIG. 7. Charge of H1 and CN (N = 1, 2, 3, and 4) atoms and total dipole
moment in debye (D) along the reaction coordinate for the H-G4×4 system.
All systems are included in the supplementary material.52
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J. Chem. Phys. 141, 134701 (2014)
produce reliable REF profiles of the system. In addition, REF
indicates that most of the electronic events are occurring in
the TS region, as indicated by the reaction force, and support-
ing W2 and W3 are mainly electronic works even if structural
changes are also taking place in the TS region.
C. Bond orders and C1 atom hybridization
Fig. 8 shows the Wiberg bond order derivatives and hy-
bridization of C1 atom along the reaction coordinate for the
G4×4 system. The highest intensity of bond order reordering
takes place in the TS region (∼1.6 Å); note that weakening
(negative derivative) and strengthening (positive derivative)
of C1 -CN (parameter associated to the surface reconstruction)
and C1 -H1 bonds, respectively, are occurring at the same time,
i.e., the process is synchronous. Moreover, from the C1 hy-
bridization profile, we can see the snappish change of sp2
to sp3 occurs at ∼1.6 Å, after the TS, the same point where
the bond order derivative reaches its maximum value. These
changes along the reaction coordinate match with the minima
of J(ξ ) and Jt (ξ ) profiles in the TS region at ∼1.6 Å. This
result indicates that at this point occurs the forming of C1 -
H1 bond, and C1 develops a sp3 hybridization, just after the
FIG. 8. Wiberg bond order derivative of C1 -H1 and C1 -CN (N = 2, 3, and
4) bonds and hybridization of C1 atom along the reaction coordinate for the
H-G4×4 system. All systems are included in the supplementary material.52
 134701-8 Cortés-Arriagada et al.
FIG. 9. Natural bond orbitals (NBOs) describing the σ bond at the
chemisorbed state. No NBO is found for the C1 -H1 bond at the TS distance,
only natural atomic orbitals (NAOs) corresponding to 2pz of C1 atom and 1s
of H1 atom.
transition state. Indeed, Fig. 9 shows that there is no NBO
associated with the C1 -H1 bond in the TS. After this point,
adsorption (or desorption) can go forward by spontaneous
charge transfer processes as discussed above. In addition,
this information from the REF profile indicates that in the
chemisorption process, graphene loses aromaticity after the
TS is established, indicating that TS is similar to the reactants.
Finally, from Fig. 10, it is interesting to note that the
high intensity in the spin density change takes place at the
same point discussed above, suggesting the midgap state of
graphene or the substrate magnetization, induced by pz va-
cancy unpaired electron on the adsorbent surface,22 is cre-
ated simultaneously with the bond weakening/strengthening
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
the reverse activation energy, which was found to be dom-
inated by electronic effects. Note that in the desorption
process, the events taking place are opposite to those dis-
cussed, i.e., change in the spin state of the adsorbent
from high to low spin, charge transfer to reach the tran-
sition state, and change in hybridization of C1 from sp3
to sp2 .
FIG. 10. Spin density derivative corresponding to the chemisorbed H atom
(H1 ).
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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
dominated by structural work (73%) associated to the sub-
strate reconstruction, while the electronic work is the great-
est contribution (67%) to desorption activation energy. On
the other hand, reaction electronic flux in combination with
the NBO electron population analysis shows that four steps
are involved in all chemisorption process: (a) intramolecular
charge redistribution in the adsorbent; (b) surface reconstruc-
tion and spontaneous charge density distribution; (c) change
in hybridization of C1 to allow formation of the C1 -H1 bond,
and substrate magnetization (midgap state of graphene) in-
duced by unpaired electron on the adsorbent surface; and
(d) final spontaneous intermolecular charge redistribution to
reach the final chemisorbed state. Note that electronic activ-
ity taking place in steps (c) and (d) explains why the des-
orption energy barrier is mainly dominated by electronic ef-
fects. In this way, reaction force and REF show to be useful
tools to study the processes whereby adsorbates interact onto
surfaces.
ACKNOWLEDGMENTS
The authors thank FONDECYT through Project Nos.
1130072, 1120093, and 1141098 and ICM Grant No. 120082
for financial support. D.C.-A. acknowledges Postdoctoral
FONDECYT Project No. 3140314 and to QTC members R.
Duran, S. Miranda, D. Ortega, and N. Villegas for useful
discussions.
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