prompt_front: Now, answer the following question based on the text below, only give me the answer and do not output any other words.

Question: How does the conduction gap depend on the strain direction?

Read the following text and answer briefly.

Context 1: \section{Introduction}

In spite of being an attractive material with excellent electronic properties \cite{ahcn09},  practical applications of graphene as in conventional semiconductor devices are still questionable due to its gapless nature  In particular, the ON/OFF current ratio is low while the saturation of current is poor in pristine graphene transistors \cite{schw10}  Many efforts of bandgap engineering in graphene \cite{yhan07,khar11,lher13,jbai10,zhan09} have been made to solve these issues  The pioneer technique proposed \cite{yhan07} is to cut 2D graphene sheets into 1D narrow nanoribons  In 2D graphene sheets, some options as Bernal-stacking of graphene on hexagonal boron nitride substrate \cite{khar11}, nitrogen-doped graphene \cite{lher13}, graphene nanomesh lattice \cite{jbai10,berr13} and Bernal-stacking bilayer graphene \cite{zhan09} have been explored  However, the possibility to open a sizable bandgap in graphene as large as those of standard semiconductors is still very unlikely  In particular, it requires a very good control of lattice geometry and edge disorder in narrow graphene nanoribbons (GNRs) \cite{quer08} and in graphene nanomesh lattices \cite{hung13}, while the bandgap opening in bilayer graphene by a perpendicular electric field may not be large enough for realistic applications \cite{fior09}  Other methods should be further verified by experiments 

\begin{figure}[!t]
\centering
\includegraphics[width=2 8in]{Fig01 pdf}
\caption{Schematic of unstrained/strained graphene junctions investigated in this work }
\label{fig_sim1}
\end{figure}

On the other hand, graphene was experimentally demonstrated to be able to sustain a much larger strain than conventional semiconductors, making it a promising candidate for flexible electronics (see in a recent review \cite{shar13})  Indeed, strain engineering has been suggested to be an alternative approach to modulating efficiently the electronic properties of graphene nanomaterials  In particular, the bandgap has periodic oscillations in the armchair GNRs \cite{ylu210} while the spin polarization at the ribbon edges (and also the bandgap) can be modulated by the strain in the zigzag cases  In 2D graphene sheets, a finite gap can open under large strains, otherwise, it may remain close to zero but the Dirac points are displaced \cite{cocc10,per209,pere09,huan10}  Many interesting electrical, optical, and magnetic properties induced by strain in graphene have been also explored, e g  see in \cite{bunc07,pere09,kuma12,per010,pell10,guin10,tlow10,zhai11} 

Besides, local strain is a good option to improve the electrical performance of graphene devices \cite{pere09,ylu010,fuji10,juan11,baha13}  For instance, it has been shown to enhance the ON current in a GNR tunneling FET \cite{ylu010} and to fortify the transport gap in GNR strained junctions \cite{baha13}  In a recent work \cite{hung14}, we have investigated the effects of uniaxial strain on the transport in 2D unstrained/strained graphene junctions and found that due to the strain-induced shift of Dirac points, a significant conduction gap of a few hundreds meV can open with a small strain of a few percent  This type of strained junction was then demonstrated to be an excellent candidate to improve the electronic operation of graphene transistors  It hence motivates us to further investigate the properties of this conduction gap so as to optimize the performance of graphene devices  On the one hand, the effects of strain should be, in principle, dependent on its applied direction  On the other hand, because the appearance of conduction gap is a consequence of the shift of Dirac points along the $k_y$-axis, it is predicted that this gap should also depend on the transport direction  Note that here, Oy (Ox) - axis is assumed to be perpendicular (parallel) to the transport direction  The effects of both strain and transport directions will be clarified systematically in the current work 

\section{Model and calculations}

In this work, the $\pi$-orbital tight binding model constructed in \cite{per209} is used to investigate the electronic transport through the graphene strained junctions schematized in Fig  1  The Hamiltonian is ${H_{tb}} = \sum\nolimits_{nm} {{t_{nm}}c_n^\dag {c_m}}$ where $t_{nm}$ is the hopping energy between nearest neighbor \emph{n}th and \emph{m}th atoms  The application of a uniaxial strain of angle $\theta$ causes the following changes in the $C-C$ bond vectors:
\begin{eqnarray}
 {{\vec r}_{nm}}\left( \sigma \right) &=& \left\{ {1 + {M_s}\left( \sigma, \theta \right)} \right\}{{\vec r}_{nm}}\left( 0 \right) \\
 {M_s}\left( \sigma, \theta \right) &=& \sigma \left[ {\begin{array}{*{20}{c}}
 {{{\cos }^2}\theta  - \gamma {{\sin }^2}\theta }&{\left( {1 + \gamma } \right)\sin \theta \cos \theta }\\
 {\left( {1 + \gamma } \right)\sin \theta \cos \theta }&{{{\sin }^2}\theta  - \gamma {{\cos }^2}\theta }
 \end{array}} \right] \nonumber
\end{eqnarray}
where $\sigma$ represents the strain and $\gamma \simeq 0 165$ is the Poisson ratio \cite{blak70}  The hopping parameters are defined as $t_{nm} \left( \sigma \right) = t_0 \exp\left[-3 37\left(r_{nm} \left( \sigma \right) /r_0 - 1\right)\right]$, where the hopping energy $t_0 = -2 7$ $eV$ and the bond length $r_{nm} \left( 0 \right) \equiv r_0 = 0 142$ $nm$ in the unstrained case  Therefore, there are three different hoping parameters $t_{1,2,3}$ corresponding to three bond vectors ${\vec r}_{1,2,3}$, respectively, in the strained graphene part of the structure (see Fig  1)  Here, we assume a 1D profile of applied strain, i e , the strain tensor is a function of position along the transport direction Ox while it is constant along the Oy-axis  The transport direction, $\phi$, and strain direction, $\theta$, are determined as schematized in Fig  1  Based on this tight binding model, two methods described below can be used to investigate the conduction gap of the considered strained junctions 

\textbf{Green's function calculations } First, we split the graphene sheet into the smallest possible unit cells periodically repeated along the Ox/Oy directions with the indices $p/q$, respectively (similarly, see the details in \cite{hung12})  The tight-binding Hamiltonian can therefore be expressed in the following form:
\begin{eqnarray}
{H_{tb}} = \sum\limits_{p,q} {\left( {{H_{p,q}} + \sum\limits_{{p_1},{q_1}} {{H_{p,q \to p_1,q_1}}} } \right)}
\end{eqnarray}
where $H_{p,q}$ is the Hamiltonian of cell $\{p,q\}$, and $H_{p,q \to p_1,q_1}$ denotes the coupling of cell $\{p,q\}$ to its nearest neighbor cell $\{p_1,q_1\}$  We then Fourier transform the operators in Eq  (2) as follows:
\begin{eqnarray}
 {c_{p,q}} = \frac{1}{{\sqrt {{M_{cell}}} }}\sum\limits_{{\kappa_y}} {{e^{i{q\kappa_y}}}} {{\hat c}_{p,{\kappa_y}}},
\end{eqnarray}
where $M_{cell}$ is the number of unit cells and $\kappa_y \equiv k_y L_y$ with the size $L_y$ of unit cells along the Oy direction  The Hamiltonian (2) is finally rewritten as a sum of $\kappa_y$-dependent 1D-components:
\begin{eqnarray}
{H_{tb}} &=& \sum\limits_{{\kappa_y}} {\hat H\left( {{\kappa_y}} \right)} \\
\hat H\left( {{\kappa_y}} \right) &=& \sum\limits_p {{{\hat H}_{p \to p - 1}}\left( {{\kappa_y}} \right) + {{\hat H}_p}\left( {{\kappa_y}} \right) + {{\hat H}_{p \to p + 1}}}\left( {{\kappa_y}} \right) \nonumber
\end{eqnarray}
With this Hamiltonian form, the Green's function formalism can be easily applied to compute transport quantities in the graphene strained junction with different transport directions  In particular, the conductance at zero temperature is determined as:
\begin{eqnarray}
 \mathcal{G} \left( \epsilon \right) = \frac{{e^2 W}}{{\pi h L_y}}\int\limits_{BZ} {d{\kappa_y} \mathcal{T}\left( {\epsilon, {\kappa_y}} \right)}
\end{eqnarray}
where $\mathcal{T}\left( {\epsilon,{\kappa_y}} \right)$ is the transmission probability computed from the Green's functions  The integration over $\kappa_y$ is performed in the whole first Brillouin zone  As in ref  \cite{hung13}, the gap of conductance (conduction gap) is then measured from the obtained data of conductance 

\textbf{Bandstructure analyses } To determine the conduction gap of strained junctions, we find that another simple way based on the analysis of graphene bandstructures could be efficiently used  It is described as follows  Since the conductance is computed from Eq  (5), the appearance of conduction gap is essentially governed by the gaps of transmission probability, which is determined from the energy gaps in the unstrained and strained graphene sections  These energy gaps can be defined directly from the graphene bandstructures  Therefore, our calculation has two steps, similar to that in \cite{hung14}  From the graphene bandstructures obtained using the tight-binding Hamiltonian above, we first look for the energy gaps $E_{unstrain}^{gap}\left( {{\kappa_y}} \right)$ and $E_{strain}^{gap}\left( {{\kappa_y}} \right)$ for a given $\kappa_y$ of two graphene sections  The maximum of these energy gaps determines the gap $E_{junc}^{gap}\left( {{\kappa_y}} \right)$ of transmission probability through the junction  Finally, the conduction gap $E_{cond gap}$ is obtained by looking for the minimum value of $E_{junc}^{gap}\left( {{\kappa_y}} \right)$ when varying $\kappa_y$ in the whole Brillouin zone 

In particular, the energy bands of strained graphene are given by
\begin{eqnarray}
 E\left( {\vec k} \right) =  \pm \left| {{t_1}{e^{i\vec k{{\vec a}_1}}} + {t_2}{e^{i\vec k{{\vec a}_2}}} + {t_3}} \right|
\end{eqnarray}
where the plus/minus sign corresponds to the conduction/valence bands, respectively  For a given direction $\phi$ of transport, in principle, the vectors $\vec L_{x,y}$ defining the sizes of unit cell along the Ox and Oy directions, respectively, can be always expressed as ${\vec L_x} = {n_1}{\vec a_1} + {n_2}{\vec a_2}$ and ${\vec L_y} = {m_1}{\vec a_1} + {m_2}{\vec a_2}$ with $\cos \phi = \frac{{{{\vec L}_x}\vec L_x^0}}{{{L_x}L_x^0}}$ and $\sin \phi = \frac{{{{\vec L}_x}\vec L_y^0}}{{{L_x}L_y^0}}$ while $\vec L_{x,y}^0 = {\vec a_1} \pm {\vec a_2}$  Note that $n_{1,2}$ and $m_{1,2}$ are integers while $\frac{{{m_1}}}{{{m_2}}} =  - \frac{{{n_1} + 2{n_2}}}{{{n_2} + 2{n_1}}}$, i e , ${\vec L_{x}} {\vec L_{y}} = 0$  In other words, we have the following expressions
\begin{eqnarray}
{{{\vec a}_1} = \frac{{ - {m_2}{{\vec L}_x} + {n_2}{{\vec L}_y}}}{{{n_2}{m_1} - {n_1}{m_2}}};\,\,\,{{\vec a}_2} = \frac{{{m_1}{{\vec L}_x} - {n_1}{{\vec L}_y}}}{{{n_2}{m_1} - {n_1}{m_2}}}}
\end{eqnarray}
On this basis, the energy bands can be rewritten in terms of $\kappa_{x, y} = \vec k \vec L_{x,y} \left( { \equiv {k_{x,y}}{L_{x,y}}} \right)$ by substituting Eqs  (7) into Eq  (6)  This new form of energy bands is finally used to compute the conduction gap of strained junctions 

As a simple example, in the case of $\phi = 0$ (armchair direction), we calculate the conduction gap as follows  First, Eq  (6) is rewritten in the form
\begin{eqnarray}
 E_{\phi = 0}\left( {\vec \kappa} \right) =  \pm \left| {{t_1}{e^{i\kappa_y/2}} + {t_2}{e^{ - i\kappa_y/2}} + {t_3}{e^{ - i\kappa_x/2}}} \right|
\end{eqnarray}
with the vectors $\vec L_{x,y} \equiv \vec L_{x,y}^0$  Using this new form, the energy gap of strained graphene for a given $\kappa_y$ is determined as
\begin{equation}
{E_{strain}^{gap}}\left( {{\kappa_y}} \right) = 2 \left| {\sqrt {{{\left( {{t_1} - {t_2}} \right)}^2} + 4{t_1}{t_2}{{\cos }^2}\frac{{{\kappa_y}}}{2}}  + {t_3}} \right|
\end{equation}
while ${E_{unstrain}^{gap}}\left( {{\kappa_y}} \right)$ is given by the same formula with $t_1$ = $t_2$ = $t_3$ $\equiv$ $t_0$  The gap of transmission probability through the junction is then determined as ${E_{junc}^{gap}}\left( {{\kappa_y}} \right) = \max \left[ {E_{unstrain}^{gap}\left( {{\kappa_y}} \right),E_{strain}^{gap}\left( {{\kappa_y}} \right)} \right]$ and, finally, the conduction gap is given by ${E_{cond gap}} = \min \left[ {E_{junc}^{gap}\left( {{\kappa_y}} \right)} \right]$ for $\kappa_y$ in the whole Brillouin zone 

We would like to notice that the Green's function calculations and the banstructure analyses give the same results of conduction gap in the junctions where the transition region between unstrained and strained graphene sections is long enough, i e , larger than about 5 to 6 nm  In the case of short length, as discussed in \cite{baha13,hung14}, this transition zone can have significant effects on the transmission between propagating states beyond the energy gaps and hence can slightly enlarge the gap of conductance, compared to the results obtained from the bandstructure calculations 

\section{Results and discussion}

\begin{figure}[!t]
\centering
\includegraphics[width=3 0in]{Fig02 pdf}
\caption{Dependence of graphene bandgap (in the unit of eV) on the applied strain and its direction: tensile (a) and compressive (b)  The radius from the central point indicates the strain strength ranging from 0 (center) to 30 $\%$ (edge of maps) while the graphene lattice is superimposed to show visibly the strain direction  The orange circle corresponds to the strains of $\sigma = 23 \%$ }
\label{fig_sim2}
\end{figure}
\begin{figure}[!t]
\centering
\includegraphics[width=3 4in]{Fig03 pdf}
\caption{Conductance ($G_0 = e^2W/hL_y$) as a function of energy in graphene strained junctions for $\sigma = 4 \%$ with different strain directions  The transport along the armchair direction ($\phi = 0$) is considered  The data obtained in a uniformly strained graphene is displayed for the comparison }
\label{fig_sim6}
\end{figure}
\begin{figure*}[!t]
\centering
\includegraphics[width=5 8in]{Fig04 pdf}
\caption{Local density of states (left panels) and corresponding transmission coefficient (right panels) for three different wave-vectors $k_y$ obtained in an unstrained/strained graphene junction of $\sigma = 4 \%$, and $\theta \equiv \phi = 0$  On the top is a schematic of graphene bandedges illustrating the strain-induced shift of Dirac points along the $k_y$-direction }
\label{fig_sim4}
\end{figure*}
\begin{figure*}[!t]
\centering
\includegraphics[width=5 6in]{Fig05 pdf}
\caption{Maps of conduction gap in unstrained/strained graphene junctions: tensile (a,c) and compressive cases (b,d)  The transport is along the armchair $\phi = 0$ (a,b) and zigzag $\phi = 30^\circ$ directions (c,d)  The strain strength ranges from 0 (center) to 6 $\%$ (edge of maps) in all cases }
\label{fig_sim4}
\end{figure*}
First, we re-examine the formation of the bandgap of graphene under a uniaxial strain  From Eq  (9), it is shown that a strain-induced finite-bandgap appears only if ${E_{strain}^{gap}}\left( {{\kappa_y}} \right) > 0$ for all $k_y$ in the first Brillouin zone, i e , ${k _y} \in \left[ { - \frac{\pi}{L_y}, \frac{\pi}{L_y}} \right]$, otherwise, the bandgap remains zero  Hence, the condition for the bandgap to be finite is either
\begin{equation*}
 \left| {{t_1} - {t_2}} \right| > \left| {{t_3}} \right|\,\,\,\,\,{\rm{OR}}\,\,\,\,\,\left| {{t_3}} \right| > \left| {{t_1} + {t_2}} \right|
\end{equation*}
and the corresponding values of bandgap are
\begin{equation*}
 {E_{gap}} = 2\left( {\left| {{t_1} - {t_2}} \right| - \left| {{t_3}} \right|} \right)\,\,\,\,\,{\rm{OR}}\,\,\,\,\,2\left( {\left| {{t_3}} \right| - \left| {{t_1} + {t_2}} \right|} \right)
\end{equation*}
This result was actually reported in \cite{per209,hase06}  We remind as displayed in Fig  2(a) that a finite bandgap opens only for strain larger than $\sim 23 \%$ and the zigzag (not armchair) is the preferred direction for bandgap opening under a tensile strain \cite{per209}  We extend our investigation to the case of compressive strain and find  (see in Fig  2(b)) that (i) the same gap threshold of $\sigma \simeq 23 \%$ is observed but (ii) the preferred direction to open the gap under a compressive strain is the armchair, not the zigzag as the case of tensile strain  This implies that the properties of graphene bandstructure at low energy should be qualitatively the same when applying strains of $\left\{ {\sigma ,\theta } \right\}$ and of $\left\{ {-\sigma ,\theta + 90^\circ} \right\}$  This feature can be understood by considering, for example, strains of $\left\{ {\sigma , \theta = 0} \right\}$ and of $\left\{ {-\sigma , \theta = 90^\circ} \right\}$  Indeed, these strains result in the same qualitative changes on the bond-lengths, i e , an increased bond-length $r_3$ and reduced bond-lengths $r_{1,2}$  However, for the same strain strength, because of the exponential dependence of hoping energies on the bond-lengths, the compressive strain generally induces a larger bandgap than the tensile one, as can be seen when comparing the data displayed in Figs  2(a) and 2(b)  To conclude, we would like to emphasize that a large strain is necessary to open a bandgap in graphene  This could be an issue for practical applications, compared to the use of graphene strained junctions explored in \cite{hung14} 

We now go to explore the properties of conduction gap in the graphene strained junctions  In Fig  3, we display the conductance as a function of energy computed from Eq  (5) using the Green's function technique  As discussed above, a small strain of a few percent (e g , 4 $\%$ here) can not change the gapless character of graphene, i e , there is no gap of conductance in the case of uniformly strained graphene  However, similar to that reported in \cite{hung14}, a significant conduction-gap of a few hundreds meV can open in the unstrained/strained graphene junctions  The appearance of this conduction gap, as mentioned previously, is due to the strain-induced shift of Dirac points and is explained as follows  Actually, the strain causes the lattice deformation and can result in the deformation of graphene bandstructure  Therefore, the bandedges as a function of wave-vector $k_y$ in unstrained and strained graphene can be illustrated schematically as in the top panel of Fig  4  As one can see, the shift of Dirac points leads to the situation where there is no value of $\kappa_y$, for which the energy gaps $E_{unstrain}^{gap}\left( {{\kappa_y}} \right)$ and $E_{strain}^{gap}\left( {{\kappa_y}} \right)$ are simultaneously equal to zero  This means that the transmission probability always shows a finite gap for any $\kappa_y$  For instance, the energy gap is zero (or small) in the unstrained (resp  strained) graphene section but finite in the strained (resp  unstrained) one in the vicinity of Dirac point $k_y = K_{unstrain}$ (resp  $K_{strain}$)  Accordingly, as illustrated in the pictures of LDOS in the left panels of Fig  4 and confirmed in the corresponding transmissions in the right panels, clear gaps of transmission are still obtained  Far from these values of $k_y$, $E_{unstrain}^{gap}\left( {{\kappa_y}} \right)$ and $E_{strain}^{gap}\left( {{\kappa_y}} \right)$ are both finite (e g , see the LDOS plotted for $k_y = K_{gap}$) and hence a finite gap of transmission also occurs  On this basis, a finite gap of conductance is achieved  More important, Fig  3 shows that besides the strength of strain, the strain effect is also strongly dependent on the applied direction  For instance, the conduction gap takes the values of $\sim$ 295, 172 and 323 meV for $\theta = 0$, $30^\circ$ and $90^\circ$, respectively 

Below, we will discuss the properties of the conduction gap with respect to the strain, its applied direction, and the direction of transport  Note that due to the lattice symmetry, the transport directions $\phi$ and $\phi + 60^\circ$ are equivalent while the applied strain of angle $\theta$ is identical to that of $\theta + 180^\circ$  Hence, the data obtained for $\phi$ ranging from $-30^\circ$ to $30^\circ$ and $\theta  \in \left[ {0^\circ ,180^\circ } \right]$ covers the properties of conduction gap in all possible cases 

In Fig  5, we present the maps of conduction gap with respect to the strain and its applied direction in two particular cases: the transport is either along the armchair ($\phi = 0$) or the zigzag ($\phi = 30^\circ$) directions  Both tensile and compressive strains are considered  Let us first discuss the results obtained in the armchair case  Figs  5(a,b) show that (i) a large conduction gap up to about 500 meV can open with a strain of 6 $\%$ and (ii) again the conduction gap is strongly $\theta$-dependent, in particular, its peaks occur at $\theta = 0$ or $90^\circ$ while the gap is zero at $\theta \approx 47^\circ$ and $133^\circ$ for tensile strain and at $\theta \approx 43^\circ$ and $137^\circ$ for compressive strain  In principle, the conduction gap is larger if the shift of Dirac points in the $\kappa_y$-axis is larger, as discussed above about Figs  3-4  We notice that the strain-induced shifts can be different for the six Dirac points of graphene \cite{kitt12} and the gap is zero when there is any Dirac point observed at the same $\kappa_y$ in the two graphene sections  From Eq  (9), we find that the Dirac points are determined by the following equations:
\begin{eqnarray*}
  {\cos}\frac{\kappa_y}{2} &=& \pm \frac{1}{2}\sqrt{\frac{{t_3^2 - {{\left( {{t_1} - {t_2}} \right)}^2}}}{{{t_1}{t_2}}}}, \\
  \cos \frac{{\kappa_x}}{2} &=& \frac{{{t_1} + {t_2}}}{{\left| {{t_3}} \right|}}\cos \frac{{\kappa_y}}{2},\,\,\,\sin \frac{{\kappa_x}}{2} = \frac{{{t_2} - {t_1}}}{{\left| {{t_3}} \right|}}\sin \frac{{\kappa_y}}{2},
\end{eqnarray*}
which simplify into ${\cos}\frac{\kappa_y}{2} = \pm \frac{1}{2}$ and, respectively, $\cos \left( {\frac{{{\kappa _x}}}{2}} \right) = \mp 1$ in the unstrained case  Hence, the zero conduction gap is obtained if
\begin{equation*}
  \frac{{t_3^2 - {{\left( {{t_1} - {t_2}} \right)}^2}}}{{4{t_1}{t_2}}} = \frac{1}{4}
\end{equation*}
Additionally, it is observed that the effects of a strain $\{\sigma,\theta\}$ are qualitatively similar to those of a strain $\{-\sigma,\theta+90^\circ\}$, i e , the peaks and zero values of conduction gap are obtained at the same $\theta$ in these two situations  To understand this, we analyze the strain matrix $M_s \left(\sigma,\theta\right)$ and find that in the case of small strains studied here, there is an approximate relationship between the bond lengths under these two strains, given by \[{r \left( \sigma, \theta \right)} - {r \left( -\sigma, \theta + 90^\circ\right)} \simeq \sigma \left( {1 - \gamma } \right) r_0,\] which is $\theta$-independent for all \emph{C-C} bond vectors  It implies that there is a fixed ratio between the hopping energies $t_i \left( \sigma, \theta \right)$ and $t_i \left( -\sigma, \theta + 90^\circ\right)$ and hence there is the similar shift of Dirac points in these two cases 
\begin{figure}[!t]
\centering
\includegraphics[width=3 4in]{Fig06 pdf}
\caption{Map showing the dependence of conduction gap on the directions ($\theta,\phi$) for $\sigma = 4 \%$  The top is a diagram illustrating the rotation of Dirac points in the \emph{k}-space with the change in the transport direction $\phi$ }
\label{fig_sim6}
\end{figure}
\begin{figure*}[!t]
\centering
\includegraphics[width=5 5in]{Fig07 pdf}
\caption{Maps of conduction gap obtained in tensile/compressive strained junctions  The transport along the armchair/zigzag directions is considered in (a,b)/(c,d), respectively  The strains $\sigma_c = -2 \%$ and $\sigma_t = 2 \%$ are applied in (a,c) while $\sigma_c = -1 \%$ and $\sigma_t = 3 \%$ in (b,d) }
\label{fig_sim4}
\end{figure*}

We now go to analyze the properties of conduction gap shown in Figs  5(c,d) where the transport is along the zigzag direction $\phi = 30^\circ$  In fact, the conduction gap in this case can reach a value as high as that of the case of $\phi = 0$ but has different $\theta$-dependence  In particular, the conduction gap has peaks at $\theta \approx 47^\circ$ and $133^\circ$ for tensile strain and at $\theta \approx 43^\circ$ and $137^\circ$ for compressive strain, where it is zero in the case of $\phi = 0$  It is also equal to zero at $\theta = 0$ and $\theta = 90^\circ$ where the peaks of conduction gap occur in the latter case of $\phi = 0$  The relationship between these two transport directions can be explained as follows  On the one hand, based on the analyses above for $\phi = 0$, we find that for a given strength of strain, a maximum shift of Dirac points along the $k_y$-axis corresponds to a minimum along the $k_x$-one and vice versa when varying the strain direction $\theta$  On the other hand, as schematized in the top of Fig  6 below, the change in the transport direction results in the rotation of the first Brillouin zone, i e , the $k_x$ (resp  $k_y$) axis in the case of $\phi = 30^\circ$ is identical to the $k_y$ (resp  $k_x$) axis in the case of $\phi = 0$  These two features explain essentially the opposite $\theta$-dependence of conduction gap for $\phi = 30^\circ$, compared to the case of $\phi = 0$ as mentioned  Again, we found the same qualitative behavior of conduction gap when applying the strains of $\{\sigma,\theta\}$ and $\{-\sigma,\theta+90^\circ\}$ 

Next, we investigate the conduction gap with respect to different transport directions $\phi$  We display a ($\theta,\phi$)-map of conduction gap for $\sigma = 4 \%$ in Fig  6 and, in the top, an additional diagram illustrating the rotation of Dirac points in the $k-$space with the change in the transport direction  It is clearly shown that (i) a similar scale of conduction gap is obtained for all different transport directions, (ii) there is a smooth and continuous shift of $E_{cond gap}-\theta$ behavior when varying $\phi$, and (iii) the same behavior of $E_{cond gap}$ is also observed when comparing the two transport directions of $\phi$ and $\phi+30^\circ$, similarly to the comparison above between $\phi = 0^\circ$ and $30^\circ$  The data plotted in Fig  6 additionally shows that $E_{cond gap}$ takes the same value in both cases of $\{\phi,\theta\}$ and $\{-\phi,-\theta\}$ with a remark that the strains of $-\theta$ and $180^\circ-\theta$ are identical  Moreover, the values of $\theta$ and $\phi$, for which the conduction gap has a peak or is equal to zero, have an almost linear relationship  In particular, the relationship for conduction gap peaks is approximately given by $\theta = \theta_A - \eta_s \phi$  For tensile strains, $\eta_s$ takes the values of $\sim 1 5667$ and $1 4333$ for $\theta_A = 0$ and $90^\circ$, respectively  On the opposite, it is about $1 4333$ and $1 5667$ for $\theta_A = 0$ and $90^\circ$, respectively, for compressive strain cases  All these features are consequences of the rotation of Dirac points in the $k$-space with respect to the transport direction $\phi$ as illustrated in the diagram on the top and the lattice symmetry of graphene 

Finally, we investigate other junctions based on compressive and tensile strained graphene sections  The idea is that in this type of strained junction, the shifts of Dirac points are different in two graphene sections of different strains, which offers the possibilities to use smaller strains to achieve a similar conduction gap, compared to the case of unstrained/strained junction  In Fig  7, we display the maps of conduction gap with respect to the directions of compressive ($\theta_c$) and tensile ($\theta_t$) strains in two cases of transport direction $\phi = 0$ (armchair) and $30^\circ$ (zigzag) for given strain strengths  Indeed, as seen in Fig  7(a,b), with smaller strains $\left\{ {{\sigma _c},{\sigma _t}} \right\} = \left\{ { - 2\% ,2\% } \right\}$ or $\left\{ { - 1\% ,3\% } \right\}$, similar conduction gap of about 310 meV can be achieved (see Figs  7(a,b)) while it requires a strain of 4 $\%$ in the unstrained/strained junctions discussed above  However, since the shift of Dirac points is strongly dependent on the direction of applied strains and the transport direction, the properties of conduction gap are more complicated than in the latter case  In particular, our calculations show that the preferred transport directions to achieve a large conduction gap are close to the armchair one  Otherwise, the conduction gap is generally smaller, similarly to the data for $\phi = 30^\circ$ compared to $\phi = 0$, as shown in Fig  7  Additionally, it is shown that the preferred directions of applied strains in the case of $\phi = 0$ are close to ${\theta _c} \equiv {\theta _t} = 0$ or $90^\circ$ 

\section{Conclusion}

Based on the tight binding calculations, we have investigated the effects of uniaxial strain on the transport properties of graphene strained junctions and discuss systematically the possibilities of achieving a large conduction gap with respect to the strain, its applied direction and the transport direction  It has been shown that due to the strain-induced deformation of graphene lattice and hence of graphene bandstructure, a finite conduction gap higher than 500 meV can be achieved for a strain of only 6 $\%$  Moreover, as a consequence of the shift of Dirac points along the $k_y$-axis, the conduction gap is strongly dependent not only on the strain strength but also on the direction of applied strain and the transport direction  A full picture of these properties of conduction gap has been presented and explained  The study hence could be a good guide for the use of this type of unstrained/strained graphene junction in electronic applications 

\textbf{\textit{Acknowledgment }} This research in Hanoi is funded by Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number 103 02-1012 42  We also acknowledges the French ANR for financial support under the projects NANOSIM-GRAPHENE (Grant no  ANR-09-NANO-016) and MIGRAQUEL (Grant no  ANR-10-BLAN-0304) 





ground_truth: Peaks occur at certain strain directions, while the gap is zero at others.

prompt_front: Now, answer the following question based on the text below, only give me the answer and do not output any other words.

Question: What are the three teams that used conflict optimization in the challenge?

Read the following text and answer briefly.

Context 2: Paper Info

Title: Conflict Optimization for Binary CSP Applied to Minimum Partition into Plane Subgraphs and Graph Coloring
Publish Date: 25 Mar 2023
Author List: Loïc Crombez (from LIMOS, Université Clermont Auvergne), Guilherme Da Fonseca (from LIS, Aix-Marseille Université), Florian Fontan (from Independent Researcher), Yan Gerard (from LIMOS, Université Clermont Auvergne), Aldo Gonzalez-Lorenzo (from LIS, Aix-Marseille Université), Pascal Lafourcade (from LIMOS, Université Clermont Auvergne), Luc Libralesso (from LIMOS, Université Clermont Auvergne), Benjamin Momège (from Independent Researcher), Jack Spalding-Jamieson (from David R  Cheriton School of Computer Science, University of Waterloo), Brandon Zhang (from Independent Researcher), Da Zheng (from Department of Computer Science, University of Illinois at Urbana-Champaign)

Figure

Figure 1: A partition of the input graph of the CG:SHOP2022 instance vispecn2518 into 57 plane graphs It is the smallest instance of the challenge with 2518 segments On top left, you see all 57 colors together On top right, you see a clique of size 57, hence the solution is optimal Each of the 57 colors is then presented in small figures 
Figure 2: Number of colors over time for the instance vispecn13806 using different values p The algorithm uses σ = 0 15, easy vertices, q max = 59022, but does not use the BDFS nor any clique 
Figure 3: Number of colors over time with different values of q max obtained on the instance vispecn13806 Parameters are σ = 0 15, p = 1 2, no clique knowledge, and no BDFS 
Figure 4: Number of colors over time with and without clique knowledge and BDFS obtained on the instance vispecn13806 Parameters are σ = 0 15, p = 1 2, and q max = 1500000 
Figure 5: Number of colors over time for the instance vispecn13806 for different values of σ In both figures the algorithm uses p = 1 2, easy vertices, q max = 59022, but does not use the BDFS nor any clique For σ ≥ 0 25, no solution better than 248 colors is found 
Figure 6: Number of colors over time (in hours) for the instance vispecn13806 
Several CG:SHOP 2022 results We compare the size of the largest known clique to the smallest coloring found by each team on a selection of 14 CG:SHOP 2022 instances 
[20][21][22][23][24][25] with state-of-the-art graph coloring algorithms The conflict optimizer underperforms except on the geometric graphs r* and dsjr* CE39-0007), SEVERITAS (ANR-20-CE39-0005) and by the French government IDEX-ISITE initiative 16-IDEX-0001 (CAP[20][21][22][23][24][25] The work of Luc Libralesso is supported by the French ANR PRC grant DECRYPT (ANR-18-CE39-0007) 

abstract

CG:SHOP is an annual geometric optimization challenge and the 2022 edition proposed the problem of coloring a certain geometric graph defined by line segments  Surprisingly, the top three teams used the same technique, called conflict optimization  This technique has been introduced in the 2021 edition of the challenge, to solve a coordinated motion planning problem 
In this paper, we present the technique in the more general framework of binary constraint satisfaction problems (binary CSP)  Then, the top three teams describe their different implementations of the same underlying strategy  We evaluate the performance of those implementations to vertex color not only geometric graphs, but also other types of graphs 

Introduction

The CG:SHOP challenge (Computational Geometry: Solving Hard Optimization Problems) is an annual geometric optimization competition, whose first edition took place in 2019  The 2022 edition proposed a problem called minimum partition into plane subgraphs  The input is a graph G embedded in the plane with edges drawn as straight line segments, and the goal is to partition the set of edges into a small number of plane graphs (Fig  )  
This goal can be formulated as a vertex coloring problem on a graph G defined as follows  The vertices of G are the segments defining the edges of G, and the edges of G correspond to pairs of crossing segments (segments that intersect only at a common endpoint are not considered crossing)  The three top-ranking teams (Lasa, Gitastrophe, and Shadoks) on the CG:SHOP 2022 challenge all used a common approach called conflict optimization while the fourth team used a SAT-Boosted Tabu Search  
Conflict optimization is a technique used by Shadoks to obtain the first place in the CG:SHOP 2021 challenge for low-makespan coordinated motion planning , and the main ideas of the technique lent themselves well to the 2022 challenge  Next, we describe the conflict optimizer as a metaheuristic to solve constraint satisfaction problems (CSP)  
We start by describing a CSP  A CSP is a triple of • variables X = (x 1 ,       , x n ), Each of the 57 colors is then presented in small figures  • domains D = (D 1 ,       , D n ), and • constraints R  Each variable x i must be assigned a value in the corresponding domain D i such that all constraints are satisfied 
In general, the constraints may forbid arbitrary subsets of values  We restrict our attention to a particular type of constraints (binary CSP ), which only involve pairs of assignments  A partial evaluation is an assignment of a subset of the variables, called evaluated, with the remaining variables called non-evaluated 
All constraints involving a non-evaluated variable are satisfied by default  We only consider assignments and partial assignments that satisfy all constraints  The conflict optimizer iteratively modifies a partial evaluation with the goal of emptying the set S of non-evaluated variables, at which point it stops 
At each step, a variable x i is removed from S  If there exists a value x ∈ D i that satisfies all constraints, then we assign the value x to the variable x i   Otherwise, we proceed as follows  For each possible value x ∈ D i , we consider the set K(i, x) of variables (other than x i ) that are part of constraints violated by the assignment x i = x 
We assign to x i the value x that minimizes where w(j) is a weight function to be described later  The variables x j ∈ K(i, x) become non-evaluated and added to S  The weight function should be such that w(j) increases each time x j is added to S, in order to avoid loops that keep moving the same variables back and forth from S  Let q(j) be the number of times x j became non-evaluated 
A possible weight function is w(j) = q(j)  More generally, we can have w(j) = q(j) p for some exponent p (typically between 1 and 2)  Of course, several details of the conflict optimizer are left open  For example, which element to choose from S, whether some random noise should be added to w, and the decision to restart the procedure from scratch after a certain time 
The CSP as is, does not apply to optimization problems  However, we can, impose a maximum value k of the objective function in order to obtain a CSP  The conflict optimizer was introduced in a low makespan coordinated motion planning setting  In that setting, the variables are the robots, the domains are their paths (of length at most k) and the constraints forbid collisions between two paths 
In the graph coloring setting, the domains are the k colors of the vertices and the constraints forbid adjacent vertices from having the same color  The conflict optimizer can be adapted to non-binary CSP, but in that case multiple variables may be unassigned for a single violated constraint  The strategy has some resemblance to the similarly named min-conflicts algorithm , but notable differences are that a partial evaluation is kept instead of an invalid evaluation and the weight function that changes over time 
While the conflict optimization strategy is simple, there are different ways to apply it to the graph coloring problem  The goal of the paper is to present how the top three teams applied it or complemented it with additional strategies  We compare the relative benefits of each variant on the instances given in the CG:SHOP 2022 challenge 
We also compare them to baselines on some instances issued from graph coloring benchmarks  The paper is organized as follows  Section 2 presents the details of the conflict optimization strategy applied to graph coloring  In the three sections that follow, the three teams Lasa, Gitastrophe, and Shadoks present the different parameters and modified strategies that they used to make the algorithm more efficient for the CG:SHOP 2022 challenge 
The last section is devoted to the experimental results 

Literature Review

The study of graph coloring goes back to the 4-color problem (1852) and it has been intensively studied since the 1970s (see for surveys)  Many heuristics have been proposed , as well as exact algorithms   We briefly present two classes of algorithms: greedy algorithms and exact algorithms  Greedy algorithms 
These algorithms are used to find good quality initial solutions in a short amount of time  The classic greedy heuristic considers the vertices in arbitrary order and colors each vertex with the smallest non-conflicting color  The two most famous modern greedy heuristics are DSATUR and Recursive Largest First (RLF )  
At each step (until all vertices are colored), DSATUR selects the vertex v that has the largest number of different colors in its neighbourhood  Ties are broken by selecting a vertex with maximum degree  The vertex v is colored with the smallest non-conflicting color  RLF searches for a large independent set I, assigns the vertices I the same color, removes I from G , and repeats until all vertices are colored 
Exact algorithms  Some exact methods use a branch-and-bound strategy, for example extending the DSATUR heuristic by allowing it to backtrack   Another type of exact method (branch-and-cut-and-price) decomposes the vertex coloring problem into an iterative resolution of two sub-problems   The "master problem" maintains a small set of valid colors using a set-covering formulation 
The "pricing problem" finds a new valid coloring that is promising by solving a maximum weight independent set problem  Exact algorithms are usually able to find the optimal coloring for graphs with a few hundred vertices  However, even the smallest CG:SHOP 2022 competition instances involve at least a few thousands vertices 

Conflict Optimization for Graph Coloring

Henceforth, we will only refer to the intersection conflict graph G induced by the instance  Vertices will refer to the vertices V (G ), and edges will refer to the edges E(G )  Our goal is to partition the vertices using a minimum set of k color classes C = {C 1 ,       , C k }, where no two vertices in the same color class C i are incident to a common edge 

Conflict Optimization

TABUCOL inspired neighbourhood One classical approach for the vertex coloring involves allowing solutions with conflicting vertices (two adjacent vertices with the same color)  It was introduced in 1987 and called TABUCOL  It starts with an initial solution, removes a color (usually the one with the least number of vertices), and assigns uncolored vertices with a new color among the remaining ones 
This is likely to lead to some conflicts (i e  two adjacent vertices sharing a same color)  The local search scheme selects a conflicting vertex, and tries to swap its color, choosing the new coloring that minimises the number of conflicts  If it reaches a state with no conflict, it provides a solution with one color less than the initial solution 
The process is repeated until the stopping criterion is met  While the original TABUCOL algorithm includes a "tabu-list" mechanism to avoid cycling, it is not always sufficient, and requires some hyper-parameter tuning in order to obtain a good performance on a large variety of instances  To overcome this issue, we use a neighbourhood, but replace the "tabu-list" by the conflict optimizer scheme presented above 
PARTIALCOL inspired neighbourhood PARTIALCOL another local search algorithm solving the vertex coloring problem was introduced in 2008  This algorithm proposes a new local search scheme that allows partial coloring (thus allowing uncolored vertices)  The goal is to minimize the number of uncolored vertices 
Similarly to TABUCOL, PARTIALCOL starts with an initial solution, removes one color (unassigning its vertices), and performs local search iterations until no vertex is left uncolored  When coloring a vertex, the adjacent conflicting vertices are uncolored  Then, the algorithm repeats the process until all vertices are colored, or the stopping criterion is met 
This neighbourhood was also introduced alongside a tabu-search procedure  The tabu-search scheme is also replaced by a conflict-optimization scheme  Note that this neighbourhood was predominantly used by the other teams 

Finding Initial Solutions

Lasa team used two approaches to find initial solutions: 1  DSATUR is the classical graph coloring algorithm presented in Section 1  2  Orientation greedy is almost the only algorithm where the geometry of the segments is used  If segments are almost parallel, it is likely that they do not intersect (thus forming an independent set) 
This greedy algorithm first sorts the segments by orientation, ranging from − π 2 to π 2   For each segment in this order, the algorithm tries to color it using the first available color  If no color has been found, a new color is created for coloring the considered segment  This algorithm is efficient, produces interesting initial solutions and takes into account the specificities of the competition 

Solution Initialization

The gitastrophe team uses the traditional greedy algorithm of Welsh and Powell to obtain initial solutions: order the vertices in decreasing order of degree, and assign each vertex the minimum-label color not used by its neighbors  During the challenge Gitastrophe attempted to use different orderings for the greedy algorithm, such as sorting by the slope of the line segment associated with each vertex (as the orientation greedy initialization presented in Section 3), and also tried numerous other strategies 
Ultimately, after running the solution optimizer for approximately the same amount of time, all initializations resulted in an equal number of colors 

Modifications to the Conflict Optimizer

Taking inspiration from memetic algorithms, which alternate between an intensification and a diversification stage, the algorithm continually switched between a phase using the above conflict score, and one minimizing only the number of conflicts  Thus during the conflict-minimization phase, the random variables f (C j ) and w(u) are both fixed equal to 1 leading to a conflict score
Each phase lasted for 10 5 iterations  Adding the conflict-minimization phase gave minor improvements to some of the challenge instances 

Shadoks

In this section, we describe the choices used by the Shadoks team for the options described in Section 2 1  The Shadoks generally chose to eliminate the color with the smallest number of elements  However, if the multistart option is toggled on, then a random color is used each time  The conflict set S is stored in a queue 
The Shadoks tried other strategies, but found that the queue gives the best results  The weight function used is w(u) = 1 + q(u) p , mostly with p = 1 2  The effect of the parameter p is shown in Fig    Notice that in all figures, the number of colors shown is the average of ten executions of the code using different random seeds 
The algorithm uses σ = 0 15, easy vertices, q max = 59022, but does not use the BDFS nor any clique  If q(u) is larger than a threshold q max , the Shadoks set w(u) = ∞ so that the vertex u never reenters S  If at some point an uncolored vertex v is adjacent to some vertex u of infinite weight in every color class, then the conflict optimizer is restarted 
When restarting, the initial coloring is shuffled by moving some vertices from their initial color class to a new one  Looking at Fig  , the value of q max does not seem to have much influence as long as it is not too small  Throughout the challenge the Shadoks almost exclusively used q max = 2000 • (75000/m) 2 , where m is the number of vertices 
This value roughly ensures a restart every few hours  q max =0 5k q max =5k q max =50k q max =100k q max =250k The Shadoks use the function f as a Gaussian random variable of mean 1 and variance σ  A good default value is σ = 0 15  The effect of the variance is shown in Fig    Notice that setting σ = 0 gives much worse results 
Option (e) The goal of BDFS is to further optimize very good solutions that the conflict optimizer is not able to improve otherwise  Fig  shows the influence of BDFS  While on this figure, the advantages of BDFS cannot be noticed, its use near the end of the challenge improved about 30 solutions  The bounded depth-first search (BDFS) algorithm tries to improve the dequeuing process 
The goal is to prevent a vertex in conflict with some adjacent colored vertices from entering in the conflict set  At the first level, the algorithm searches for a recoloring of some adjacent vertices which allows us to directly recolor the conflict vertex  If no solution is found, the algorithm  In both figures the algorithm uses p = 1 2, easy vertices, q max = 59022, but does not use the BDFS nor any clique 
For σ ≥ 0 25, no solution better than 248 colors is found  could recolor some vertices at larger distances from the conflict vertex  To do so, a local search is performed by trying to recolor vertices at a bounded distance from the conflict vertex in the current partial solution  The BDFS algorithm has two parameters: adjacency bound a max and depth d 
In order to recolor a vertex v, BDFS gets the set C of color classes with at most a max neighbors of v  If a class in C has no neighbor of v, v is assigned to C  Otherwise, for each class C ∈ C, BDFS tries to recolor the vertices in C which are adjacent to v by recursively calling itself with depth d − 1 
At depth d = 0 the algorithm stops trying to color the vertices  During the challenge the Shadoks used BDFS with parameters a max = 3 and d = 3  The depth was increased to 5 (resp  7) when the number of vertices in the queue was 2 (resp  1)  Degeneracy order Given a target number of colors k, we call easy vertices a set of vertices Y such that, if the remainder of the vertices of G are colored using k colors, then we are guaranteed to be able to color all vertices of G with k colors 
This is obtained using the degeneracy order Y   To obtain Y we iteratively remove from the graph a vertex v that has at most k − 1 neighbors, appending v to the end of Y   We repeat until no other vertex can be added to Y   Notice that, once we color the remainder of the graph with at least k colors, we can use a greedy coloring for Y in order from last to first without increasing the number of colors used 
Removing the easy vertices reduces the total number of vertices, making the conflict optimizer more effective  The Shadoks always toggle this option on (the challenge instances contain from 0 to 23% easy vertices) 

Results

We provide the results of the experiments performed with the code from the three teams on two classes of instances  First, we present the results on some selected CG:SHOP 2022 instances  These instances are intersection graphs of line segments  Second, we execute the code on graphs that are not intersection graphs, namely the classic DIMACS graphs , comparing the results of our conflict optimizer implementations to previous solutions 
The source code for the three teams is available at: • Lasa: https://github com/librallu/dogs-color • Gitastrophe: https://github com/jacketsj/cgshop2022-gitastrophe • Shadoks: https://github com/gfonsecabr/shadoks-CGSHOP2022

CG:SHOP 2022 Instances

We selected 14 instances (out of 225) covering the different types of instances given in the CG:SHOP 2022 challenge  The results are presented in Table   For comparison, we executed the HEAD code on some instances using the default parameters  The table shows the smallest number of colors for which HEAD found a solution 
We ran HEAD for 1 hour of repetitions for each target number of colors on a single CPU core (the HEAD solver takes the target number of colors as a parameter and we increased this parameter one by one)  At the end of the challenge, 8 colorings computed by Lasa, 11 colorings computed by Gitastrophe, and 23 colorings computed by Shadoks over 225 instances have been proved optimal (their number of colors is equal to the size of a clique) 
In order to compare the efficiency of the algorithms, we executed the different implementations on the CG:SHOP instance vispecn13806  The edge density of this graph is 19%, the largest clique that we found has 177 vertices and the best coloring found during the challenge uses 218 colors  Notice that vispecn13806 is the same instance used in other Shadoks experiments in Section 5  Notice also that HEAD algorithm provides 283 colors after one hour compared to less than 240 colors for the conflict optimizers 
We ran the three implementations on three different servers and compared the results shown in Figure   For each implementation, the x coordinate is the running time in hours, while the y coordinate is the smallest number of colors found at that time 

Results on DIMACS Graphs

We tested the implementation of each team on the DIMACS instances to gauge the performance of the conflict optimizer on other classes of graphs  We compared our results to the best known bounds and to the state of the art coloring algorithms HEAD and QACOL   The time limit for Lasa's algorithms is 1 hour 
CWLS is Lasa's conflict optimizer with the neighbourhood presented in TABUCOL , while PWLS is the optimizer with the neighbourhood presented in PARTIALCOL   Gitastrophe algorithm ran 10 minutes after which the number of colors no longer decreases  Shadoks algorithm ran for 1 hour without the BDFS option (results with BDFS are worse) 
Results are presented in Table   We only kept the difficult DIMACS instances  For the other instances, all the results match the best known bounds  The DIMACS instances had comparatively few edges (on the order of thousands or millions); the largest intersection graphs considered in the CG:SHOP challenge had over 1 5 billion edges 
We notice that the conflict optimizer works extremely poorly on random graphs, but it is fast and appears to perform well on geometric graphs (r250 5, r1000 1c, r1000 5, dsjr500 1c and dsjr500 5), matching the best-known results   Interestingly, these geometric graphs are not intersection graphs as in the CG:SHOP challenge, but are generated based on a distance threshold 
On the DIMACS graphs, Lasa implementation shows better performance than the other implementations 
Context 3: Paper Info

Title: Bistability between π-diradical open-shell and closed-shell states in indeno[1,2-a]fluorene
Publish Date: Unkown
Author List: Shantanu Mishra (from IBM Research Europe -Zurich), Manuel Vilas-Varela (from Department of Organic Chemistry, Center for Research in Biological Chemistry and Molecular Materials (CiQUS), University of Santiago de Compostela), Leonard-Alexander Lieske (from IBM Research Europe -Zurich), Ricardo Ortiz (from Donostia International Physics Center (DIPC)), Igor Rončević (from Department of Chemistry, University of Oxford), Florian Albrecht (from IBM Research Europe -Zurich), Diego Peña (from Department of Organic Chemistry, Center for Research in Biological Chemistry and Molecular Materials (CiQUS), University of Santiago de Compostela), Leo Gross (from IBM Research Europe -Zurich)

Figure

Fig  1 | Non-benzenoid non-alternant polycyclic conjugated hydrocarbons a, Classical nonbenzenoid non-alternant polycyclic conjugated hydrocarbons: pentalene, azulene and heptalene b, Generation of indacenes and indenoindenes through benzinterposition and benzannelation of pentalene, respectively Gray filled rings represent Clar sextets c, Closed-shell Kekulé (left) and openshell non-Kekulé (right) resonance structures of QDMs Note that meta-QDM is a non-Kekulé molecule All indenofluorene isomers, being derived through benzannelation of indacenes, contain a central QDM moiety d, Closed-shell Kekulé (top) and open-shell non-Kekulé (bottom) resonance structures of indenofluorenes Compared to their closed-shell structures, 1 and 5 gain two Clar sextets in the openshell structure, while 2-4 gain only one Clar sextet in the open-shell structure Colored bonds in d highlight the ortho-and para-QDM moieties in the two closed-shell Kekulé structures of 5  e, Scheme of on-surface generation of 5 by voltage pulse-induced dehydrogenation of 6 (C20H14) Structures 7 and 8 represent the two monoradical species (C20H13) 
Fig  2 | Characterization of open-shell indeno[1,2-a]fluorene on bilayer NaCl/Au(111) a, DFTcalculated wave functions of the frontier orbitals of 5OS in the triplet configuration for the spin up (occupied) level (isovalue: 0 002 e -Å -3 ) Blue and red colors represent opposite phases of the wave function b, Corresponding DFT-calculated spin density of 5OS (isovalue: 0 01 e -Å -3) Blue and orange colors represent spin up and spin down densities, respectively c, Probability density of the SOMOs of 5OS (isovalue: 0 001 e -Å -3 ) d, DFT-calculated bond lengths of 5OS e, Constant-height I(V) spectra acquired on a species of 5 assigned as 5OS, along with the corresponding dI/dV(V) spectra Open feedback parameters: V = -2 V, I = 0 17 pA (negative bias side) and V = 2 V, I = 0 17 pA (positive bias side) Acquisition position of the spectra is shown in Supplementary Fig 7 f, Scheme of many-body transitions associated to the measured ionic resonances of 5OS Also shown are STM images of assigned 5OS at biases where the corresponding transitions become accessible Scanning parameters: I = 0 3 pA (V = -1 2V and -1 5 V) and 0 2 pA (V = 1 3 V and 1 6 V)  g, Laplace-filtered AFM image of assigned 5OS STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 3Å The tip-height offset Δz for each panel is provided with respect to the STM setpoint, and positive (negative) values of Δz denote tip approach (retraction) from the STM setpoint f and g show the same molecule at the same adsorption site, which is next to a trilayer NaCl island The bright and dark features in the trilayer NaCl island in g correspond to Cl -and Na + ions, respectively Scale bars: 10 Å (f) and 5 Å (g) 
Fig  3 | Characterization of closed-shell indeno[1,2-a]fluorene on bilayer NaCl/Au(111) a, DFTcalculated wave functions of the frontier orbitals of closed-shell 5 0 (isovalue: 0 002 e -Å -3 ) The wave functions shown here are calculated for the 5para geometry b, DFT-calculated bond lengths of 5ortho (top) and 5para (bottom) c, Constant-height I(V) spectra acquired on a species of 5 assigned as 5para, along with the corresponding dI/dV(V) spectra Open feedback parameters: V = -2 V, I = 0 15 pA (negative bias side) and V = 2 2 V, I = 0 15 pA (positive bias side) Acquisition position of the spectra is shown in Supplementary Fig  7  d, Scheme of many-body transitions associated to the measured ionic resonances of 5para Also shown are STM images of assigned 5para at biases where the corresponding transitions become accessible Scanning parameters: I = 0 15 pA (V = -1 5 V) and 0 2 pA (V = 1 7 V)  e, Laplace-filtered AFM image of assigned 5para STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 7 Å  f, Selected bonds labeled for highlighting bond order differences between 5para and 5ortho For the bond pairs a/b, c/d and e/f, the bonds labeled in bold exhibit a higher bond order than their neighboring labeled bonds in 5para g, Laplace-filtered AFM images of 5 on bilayer NaCl/Cu(111) showing switching between 5OS and 5para as the molecule changes its adsorption position The faint protrusion adjacent to 5 is a defect that stabilizes the adsorption of 5  STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 3Å  STM and STS data in c and d are acquired on the same species, while the AFM data in e is acquired on a different species Scale bars: 10 Å (d) and 5 Å (e,g) 
NMR (300 MHz, CDCl3) δ: 7 51 (m, 2H), 7 40 -7 28 (m, 5H), 7 27 -7 20 (m, 2H), 7 13 (d, J = 7 7 Hz, 1H), 2 07 (s, 3H), 1 77 (s, 3H) ppm  13C NMR-DEPT (75 MHz, CDCl3, 1:1 mixture of atropisomers) δ: 141 2 (C), 141 1 (C), 140 0 (C), 139 4 (2C), 137 5 (C), 137 4 (C), 136 0 (3C), 134 8 (C), 134 5 (C), 134 1 (C), 134 0 (C), 133 7 (C), 133 6 (C), 131 6 (CH), 131 2 (CH), 131 1 (CH), 130 7 (CH), 129 8 (CH), 129 7 (CH), 129 5 (CH), 129 4 (CH), 129 0 (CH), 128 9 (CH), 128 7 (2CH), 128 6 (2CH), 127 2 (CH), 127 1 (CH), 127 0 (CH), 126 9 (CH), 126 7 (CH), 126 6 (CH), 20 6 (CH3), 20 5 (CH3), 17 7 (CH3), 17 5 (CH3) ppm MS (APCI) m/z (%): 327 (M+1, 100) HRMS: C20H16Cl2; calculated: 327 0702, found: 327 0709 
NMR (500 MHz, CDCl3) δ: 7 93 (d, J = 7 6 Hz, 1H), 7 85 (d, J = 7 5 Hz, 1H), 7 78 (d, J = 7 7 Hz, 1H), 7 65 (d, J = 7 4 Hz, 1H), 7 61 (d, J = 7 5 Hz, 1H), 7 59 (d, J = 7 7 Hz, 1H), 7 47 (ddd, J = 8 4, 7 2, 1 1 Hz, 1H), 7 42 (dd, J = 8 1, 7 0 Hz, 1H), 7 35 (m, 2H), 4 22 (s, 3H), 4 02 (s, 3H) ppm  13C NMR-DEPT (125 MHz, CDCl3) δ: 144 1 (C), 143 3 (C), 142 3 (C), 141 9 (C), 141 8 (C), 141 2 (C), 138 2 (C), 136 5 (C), 127 0 (CH), 126 9 (CH), 126 7 (CH), 126 6 (CH), 125 3 (CH), 125 2 (CH), 123 6 (CH), 122 2 (CH), 119 9 (CH), 118 4 (CH), 37 4 (CH2), 36 3 (CH2) ppm MS (APCI) m/z (%): 254 (M+, 88) HRMS: C20H14; calculated: 254 1090, found: 254 1090 

abstract

Indenofluorenes are non-benzenoid conjugated hydrocarbons that have received great interest owing to their unusual electronic structure and potential applications in nonlinear optics and photovoltaics  Here, we report the generation of unsubstituted indeno[1,2-a]fluorene, the final and yet unreported parent indenofluorene regioisomer, on various surfaces by cleavage of two C-H bonds in 7,12-dihydro indeno[1,2-a]fluorene through voltage pulses applied by the tip of a combined scanning tunneling microscope and atomic force microscope 
On bilayer NaCl on Au(111), indeno[1,2a]fluorene is in the neutral charge state, while it exhibits charge bistability between neutral and anionic states on the lower work function surfaces of bilayer NaCl on Ag(111) and Cu(111)  In the neutral state, indeno[1,2-a]fluorene exhibits either of two ground states: an open-shell π-diradical state, predicted to be a triplet by density functional and multireference many-body perturbation theory calculations, or a closedshell state with a para-quinodimethane moiety in the as-indacene core 
Switching between open-and closed-shell states of a single molecule is observed by changing its adsorption site on NaCl  The inclusion of non-benzenoid carbocyclic rings is a viable route to tune the physicochemical properties of polycyclic conjugated hydrocarbons (PCHs)   Non-benzenoid polycycles may lead to local changes in strain, conjugation, aromaticity, and, relevant to the context of the present work, induce an open-shell ground state of the corresponding PCHs  
Many nonbenzenoid PCHs are also non-alternant, where the presence of odd-membered polycycles breaks the bipartite symmetry of the molecular network   Figure shows classical examples of non-benzenoid non-alternant PCHs, namely, pentalene, azulene and heptalene  Whereas azulene is a stable PCH exhibiting Hückel aromaticity ([4n+2] π-electrons, n = 2), pentalene and heptalene are unstable Hückel antiaromatic compounds with [4n] π-electrons, n = 2 (pentalene) and n = 3 (heptalene) 
Benzinterposition of pentalene generates indacenes, consisting of two isomers s-indacene and as-indacene (Fig  )  Apart from being antiaromatic, indacenes also contain proaromatic quinodimethane (QDM) moieties (Fig  ) , which endows them with potential open-shell character  While the parent s-indacene and asindacene have never been isolated, stable derivatives of s-indacene bearing bulky substituents have been synthesized  
A feasible strategy to isolate congeners of otherwise unstable non-benzenoid non-alternant PCHs is through fusion of benzenoid rings at the ends of the π-system, that is, benzannelation  For example, while the parent pentalene is unstable, the benzannelated congener indeno[2,1-a]indene is stable under ambient conditions (Fig  )  
However, the position of benzannelation is crucial for stability: although indeno[2,1a]indene is stable, its regioisomer indeno[1,2-a]indene (Fig  ) oxidizes under ambient conditions   Similarly, benzannelation of indacenes gives rise to the family of PCHs known as indenofluorenes (Fig  ), which constitute the topic of the present work 
Depending on the benzannelation position and the indacene core, five regioisomers can be constructed, namely, indeno [ Practical interest in indenofluorenes stems from their low frontier orbital gap and excellent electrochemical characteristics that render them as useful components in organic electronic devices  
The potential open-shell character of indenofluorenes has led to several theoretical studies on their use as non-linear optical materials and as candidates for singlet fission in organic photovoltaics   Recent theoretical work has also shown that indenofluorene-based ladder polymers may exhibit fractionalized excitations 
Fundamentally, indenofluorenes represent model systems to study the interplay between aromaticity and magnetism at the molecular scale   Motivated by many of these prospects, the last decade has witnessed intensive synthetic efforts toward the realization of indenofluorenes  Derivatives of 1-4 have been realized in solution , while 1-3 have also been synthesized on surfaces and characterized using scanning tunneling microscopy (STM) and atomic force microscopy (AFM), which provide information on molecular orbital densities , molecular structure and oxidation state  
With regards to the open-shell character of indenofluorenes, 2-4 are theoretically and experimentally interpreted to be closed-shell, while calculations indicate that 1 and 5 should exhibit open-shell ground states   Bulk characterization of mesitylsubstituted 1, including X-ray crystallography, temperature-dependent NMR, and electron spin resonance spectroscopy, provided indications of its open-shell ground state  
Electronic characterization of 1 on Au(111) surface using scanning tunneling spectroscopy (STS) revealed a low electronic gap of 0 4 eV (ref  )  However, no experimental proof of an openshell ground state of 1 on Au(111), such as detection of singly occupied molecular orbitals (SOMOs) or spin excitations and correlations due to unpaired electrons , was shown 
In this work, we report the generation and characterization of unsubstituted 5  Our research is motivated by theoretical calculations that indicate 5 to exhibit the largest diradical character among all indenofluorene isomers   The same calculations also predict that 5 should possess a triplet ground state 
Therefore, 5 would qualify as a Kekulé triplet, of which only a handful of examples exist   However, definitive synthesis of 5 has never been reported so far  Previously, Dressler et al  reported transient isolation of mesityl-substituted 5, where it decomposed both in the solution and in solid state , and only the structural proof of the corresponding dianion was obtained 
On-surface generation of a derivative of 5, starting from truxene as a precursor, was recently reported   STM data on this compound, containing the indeno[1,2-a]fluorene moiety as part of a larger PCH, was interpreted to indicate its open-shell ground state  However, the results did not imply the ground state of unsubstituted 5  Here, we show that on insulating surfaces 5 can exhibit either of two ground states: an open-shell or a closed-shell 
We infer the existence of these two ground states based on high-resolution AFM imaging with bond-order discrimination and STM imaging of molecular orbital densities   AFM imaging reveals molecules with two different geometries  Characteristic bond-order differences in the two geometries concur with the geometry of either an open-or a closed-shell state 
Concurrently, STM images at ionic resonances show molecular orbital densities corresponding to SOMOs for the open-shell geometry, but orbital densities of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for the closed-shell geometry  Our experimental results are in good agreement with density functional theory (DFT) and multireference perturbation theory calculations 
Finally, we observe switching between open-and closed-shell states of a single molecule by changing its adsorption site on the surface  Synthetic strategy toward indeno[1,2-a]fluorene  The generation of 5 relies on the solution-phase synthesis of the precursor 7,12-dihydro indeno[1,2-a]fluorene (6)  Details on synthesis and characterization of 6 are reported in Supplementary Figs 
  Single molecules of 6 are deposited on coinage metal (Au(111), Ag(111) and Cu(111)) or insulator surfaces  In our work, insulating surfaces correspond to two monolayer-thick (denoted as bilayer) NaCl on coinage metal surfaces  Voltage pulses ranging between 4-6 V are applied by the tip of a combined STM/AFM system, which result in cleavage of one C-H bond at each of the pentagonal apices of 6, thereby leading to the generation of 5 (Fig  ) 
In the main text, we focus on the generation and characterization of 5 on insulating surfaces  Generation and characterization of 5 on coinage metal surfaces is shown in Supplementary Fig    )  Blue and orange colors represent spin up and spin down densities, respectively  c, Probability density of the SOMOs of 5OS (isovalue: 0 001 e -Å -3 ) 
d, DFT-calculated bond lengths of 5OS  e, Constant-height I(V) spectra acquired on a species of 5 assigned as 5OS, along with the corresponding dI/dV(V) spectra  Open feedback parameters: V = -2 V, I = 0 17 pA (negative bias side) and V = 2 V, I = 0 17 pA (positive bias side)  Acquisition position of the spectra is shown in Supplementary Fig    f, Scheme of many-body transitions associated to the measured ionic resonances of 5OS 
Also shown are STM images of assigned 5OS at biases where the corresponding transitions become accessible  Scanning parameters: I = 0 3 pA (V = -1 2 V and -1 5 V) and 0 2 pA (V = 1 3 V and 1 6 V)  g, Laplace-filtered AFM image of assigned 5OS  STM set point: V = 0 2 V, I = 0 5 pA on bilayer NaCl, Δz = -0 3
Å  The tip-height offset Δz for each panel is provided with respect to the STM setpoint, and positive (negative) values of Δz denote tip approach (retraction) from the STM setpoint  f and g show the same molecule at the same adsorption site, which is next to a trilayer NaCl island  The bright and dark features in the trilayer NaCl island in g correspond to Cl -and Na + ions, respectively 
Scale bars: 10 Å (f) and 5 Å (g)  To experimentally explore the electronic structure of 5, we used bilayer NaCl films on coinage metal surfaces to electronically decouple the molecule from the metal surfaces  Before presenting the experimental findings, we summarize the results of our theoretical calculations performed on 5 in the neutral charge state (denoted as 5 0 ) 
We start by performing DFT calculations on 5 0 in the gas phase  Geometry optimization performed at the spin-unrestricted UB3LYP/6-31G level of theory leads to one local minimum, 5OS, the geometry of which corresponds to the open-shell resonance structure of 5 (Fig  , the label OS denotes open-shell) 
The triplet electronic configuration of 5OS is the lowest-energy state, with the openshell singlet configuration 90 meV higher in energy  Geometry optimization performed at the restricted closed-shell RB3LYP/6-31G level reveals two local minima, 5para and 5ortho, the geometries of which (Fig  ) exhibit bond length alternations in line with the presence of a para-or an ortho-QDM moiety, respectively, in the as-indacene core of the closed-shell resonance structures of 5 (Fig  )  
Relative to 5OS in the triplet configuration, 5para and 5ortho are 0 40 and 0 43 eV higher in energy, respectively  Additional DFT results are shown in Supplementary Fig    To gain more accurate insights into the theoretical electronic structure of 5, we performed multireference perturbation theory calculations (Supplementary Fig  ) based on quasi-degenerate second-order n-electron valence state perturbation theory (QD-NEVPT2) 
In so far as the order of the ground and excited states are concerned, the results of QD-NEVPT2 calculations qualitatively match with DFT calculations  For 5OS, the triplet configuration remains the lowest-energy state, with the open-shell singlet configuration 60 meV higher in energy  The energy differences between the open-and closed-shell states are substantially reduced in QD-NEVPT2 calculations, with 5para and 5ortho only 0 11 and 0 21 eV higher in energy, respectively, compared to 5OS in the triplet configuration 
We also performed nucleus-independent chemical shift calculations to probe local aromaticity of 5 in the openand closed-shell states  While 5OS in the triplet configuration exhibits local aromaticity at the terminal benzenoid rings, 5OS in the open-shell singlet configuration, 5para and 5ortho all display antiaromaticity (Supplementary Fig  ) 
The choice of the insulating surface determines the charge state of 5: while 5 adopts neutral charge state on the high work function bilayer NaCl/Au(111) surface (irrespective of its openor closed-shell state, Supplementary Fig  ), 5 exhibits charge bistability between 5 0 and the anionic state 5 -1 on the lower work function bilayer NaCl/Ag(111) and Cu(111) surfaces (Supplementary Figs  ) 
In the main text, we focus on the characterization of 5 on bilayer NaCl/Au(111)  Characterization of charge bistable 5 is reported in Supplementary Figs    We first describe experiments on 5 on bilayer NaCl/Au(111), where 5 exhibits a geometry corresponding to the calculated 5OS geometry, and an open-shell electronic configuration 
We compare the experimental data on this species to calculations on 5OS with a triplet configuration, as theory predicts a triplet ground state for 5OS  For 5OS, the calculated frontier orbitals correspond to the SOMOs ψ1 and ψ2 (Fig  ), whose spin up levels are occupied and the spin down levels are empty 
Figure shows the DFT-calculated bond lengths of 5OS, where the two salient features, namely, the small difference in the bond lengths within each ring and the notably longer bond lengths in the pentagonal rings, agree with the open-shell resonance structure of 5 (Fig  )  Figure shows an AFM image of 5 adsorbed on bilayer NaCl/Au(111) that we assign as 5OS, where the bond-order differences qualitatively correspond to the calculated 5OS geometry (discussed and compared to the closed-shell state below) 
Differential conductance spectra (dI/dV(V), where I and V denote the tunneling current and bias voltage, respectively) acquired on assigned 5OS exhibit two peaks centered at -1 5 V and 1 6 V (Fig  ), which we assign to the positive and negative ion resonances (PIR and NIR), respectively  Figure shows the corresponding STM images acquired at the onset (V = -1 2
V/1 3 V) and the peak (V = -1 5 V/1 6 V) of the ionic resonances  To draw a correspondence between the STM images and the molecular orbital densities, we consider tunneling events as many-body electronic transitions between different charge states of 5OS (Fig  )  Within this framework, the PIR corresponds to transitions between 5 0 and the cationic state 5  
At the onset of the PIR at -1 2 V, an electron can only be detached from the SOMO ψ1 and the corresponding STM image at -1 2 V shows the orbital density of ψ1  Increasing the bias to the peak of the PIR at -1 5 V, it becomes possible to also empty the SOMO ψ2, such that the corresponding STM image shows the superposition of ψ1 and ψ2, that is, |ψ1| 2 + |ψ2| 2 (ref 
)  Similarly, the NIR corresponds to transitions between 5 0 and 5 -1   At the NIR onset of 1 3 V, only electron attachment to ψ2 is energetically possible  At 1 6 V, electron attachment to ψ1 also becomes possible, and the corresponding STM image shows the superposition of ψ1 and ψ2  The observation of the orbital densities of SOMOs, and not the hybridized HOMO and LUMO, proves the open-shell ground state of assigned 5OS 
Measurements of the monoradical species with a doublet ground state are shown in Supplementary Fig    Unexpectedly, another species of 5 was also experimentally observed that exhibited a closedshell ground state  In contrast to 5OS, where the frontier orbitals correspond to the SOMOs ψ1 and ψ2, DFT calculations predict orbitals of different shapes and symmetries for 5para and 5ortho, denoted as α and β and shown in Fig   
For 5ortho, α and β correspond to HOMO and LUMO, respectively  The orbitals are inverted in energy and occupation for 5para, where β is the HOMO and α is the LUMO  Fig  shows an AFM image of 5 that we assign as 5para  We experimentally infer its closed-shell state first by using qualitative bond order discrimination by AFM 
In high-resolution AFM imaging, chemical bonds with higher bond order are imaged brighter (that is, with higher frequency shift Δf) due to stronger repulsive forces, and they appear shorter   In Fig  , we label seven bonds whose bond orders show significant qualitative differences in the calculated 5ortho, 5para (Fig  ) and 5OS (Fig  ) geometries 
In 5para, the bonds b and d exhibit a higher bond order than a and c, respectively  This pattern is reversed for 5ortho, while the bond orders of the bonds a-d are all similar and small for 5OS  Furthermore, in 5para bond f exhibits a higher bond order than e, while in 5ortho and 5OS bonds e and f exhibit similar bond order (because they belong to Clar sextets) 
Finally, the bond labeled g shows a higher bond order in 5para than in 5ortho and 5OS  The AFM image of assigned 5para shown in Fig  indicates higher bond orders of the bonds b, d and f compared to a, c and e, respectively  In addition, the bond g appears almost point-like and with enhanced Δf contrast compared to its neighboring bonds, indicative of a high bond order (see Supplementary Fig  for height-dependent measurements) 
These observations concur with the calculated 5para geometry (Fig  )  Importantly, all these distinguishing bond-order differences are distinctly different in the AFM image of 5OS shown in Fig  , which is consistent with the calculated 5OS geometry (Fig  )  In the AFM images of 5OS (Fig  and Supplementary Fig  ), the bonds a-d at the pentagon apices appear with similar contrast and apparent bond length 
The bonds e and f at one of the terminal benzenoid rings also exhibit similar contrast and apparent bond length, while the central bond g appears longer compared to assigned 5para  Further compelling evidence for the closed-shell state of assigned 5para is obtained by STM and STS  dI/dV(V) spectra acquired on an assigned 5para species exhibit two peaks centered at -1 4 V (PIR) and 1 6 V (NIR) (Fig  ) 
STM images acquired at these biases (Fig  ) show the orbital densities of β (-1 4 V) and α (1 6 V)  First, the observation of α and β as the frontier orbitals of this species, and not the SOMOs, strongly indicates its closed-shell state  Second, consistent with AFM measurements that indicate good correspondence to the calculated 5para geometry, we observe β as the HOMO and α as the LUMO 
For 5ortho, α should be observed as the HOMO and β as the LUMO  We did not observe molecules with the signatures of 5ortho in our experiments  We observed molecules in open-(5OS, Fig  ) and closed-shell (5para, Fig  ) states in similar occurrence after their generation from 6 on the surface  We could also switch individual molecules between open-and closed-shell states as shown in Fig  and Supplementary Fig   
To this end, a change in the adsorption site of a molecule was induced by STM imaging at ionic resonances, which often resulted in movement of the molecule  The example presented in Fig  shows a molecule that was switched from 5para to 5OS and back to 5para  The switching is not directed, that is, we cannot choose which of the two species will be formed when changing the adsorption site, and we observed 5OS and 5para in approximately equal yields upon changing the adsorption site 
The molecule in Fig  is adsorbed on top of a defect that stabilizes its adsorption geometry on bilayer NaCl  At defect-free adsorption sites on bilayer NaCl, that is, without a third layer NaCl island or atomic defects in the vicinity of the molecule, 5 could be stably imaged neither by AFM nor by STM at ionic resonances (Supplementary Fig  ) 
Without changing the adsorption site, the state of 5 (open-or closedshell) never changed, including the experiments on bilayer NaCl/Ag(111) and Cu(111), on which the charge state of 5 could be switched (Supplementary Figs  )  Also on these lower work function surfaces, both open-and closed-shell species were observed for 5 0 and both showed charge bistability between 5 0 (5OS or 5para) and 5 -1 (Supplementary Figs  ) 
The geometrical structure of 5 -1 probed by AFM, and its electronic structure probed by STM imaging at the NIR (corresponding to transitions between 5 -1 and the dianionic state 5 -2 ), are identical within the measurement accuracy for the charged species of both 5OS and 5para  When cycling the charge state of 5 between 5 0 and 5 -1 several times, we always observed the same state (5OS or 5para) when returning to 5 0 , provided the molecule did not move during the charging/discharging process 
Based on our experimental observations we conclude that indeno[1,2-a]fluorene (5), the last unknown indenofluorene isomer, can be stabilized in and switched between an open-shell (5OS) and a closed-shell (5para) state on NaCl  For the former, both DFT and QD-NEVPT2 calculations predict a triplet electronic configuration 
Therefore, 5 can be considered to exhibit the spin-crossover effect, involving magnetic switching between high-spin (5OS) and low-spin (5para) states, coupled with a reversible structural transformation  So far, the spin-crossover effect has mainly only been observed in transition-metal-based coordination compounds with a near-octahedral geometry  
The observation that the switching between open-and closedshell states is related to changes in the adsorption site but is not achieved by charge-state cycling alone, indicates that the NaCl surface and local defects facilitate different electronic configurations of 5 depending on the adsorption site 
Gas-phase QD-NEVPT2 calculations predict that 5OS is the ground state, and the closed-shell 5para and 5ortho states are 0 11 and 0 21 eV higher in energy  The experiments, showing bidirectional switching between 5OS and 5para, indicate that a change in the adsorption site can induce sufficient change in the geometry of 5 (leading to a corresponding change in the ground state electronic configuration) and thus induce switching 
Switching between open-and closed-shell states in 5 does not require the breaking or formation of covalent bonds , but a change of adsorption site on NaCl where the molecule is physisorbed  Our results should have implications for single-molecule devices, capitalizing on the altered electronic and chemical properties of a system in π-diradical open-shell and closed-shell states such as frontier orbital and singlet-triplet gaps, and chemical reactivity 
For possible future applications as a single-molecule switch, it might be possible to also switch between open-and closed-shell states by changing the local electric field, such as by using chargeable adsorbates   Scanning probe microscopy measurements and sample preparation  STM and AFM measurements were performed in a home-built system operating at base pressures below 1×10 -10 mbar and a base temperature of 5 K  Bias voltages are provided with respect to the sample 
All STM, AFM and spectroscopy measurements were performed with carbon monoxide (CO) functionalized tips  AFM measurements were performed in non-contact mode with a qPlus sensor   The sensor was operated in frequency modulation mode with a constant oscillation amplitude of 0 5 Å  STM measurements were performed in constantcurrent mode, AFM measurements were performed in constant-height mode with V = 0 V, and I(V) and Δf(V) spectra were acquired in constant-height mode 
Positive (negative) values of the tip-height offset Δz represent tip approach (retraction) from the STM setpoint  All dI/dV(V) spectra are obtained by numerical differentiation of the corresponding I(V) spectra  STM and AFM images, and spectroscopy curves, were post-processed using Gaussian low-pass filters 
Au(111), Ag(111) and Cu(111) surfaces were cleaned by iterative cycles of sputtering with Ne + ions and annealing up to 800 K  NaCl was thermally evaporated on Au(111), Ag(111) and Cu(111) surfaces held at 323 K, 303 K and 283 K, respectively  This protocol results in the growth of predominantly bilayer (100)-terminated islands, with a minority of trilayer islands 
Sub-monolayer coverage of 6 on surfaces was obtained by flashing an oxidized silicon wafer containing the precursor molecules in front of the cold sample in the microscope  CO molecules for tip functionalization were dosed from the gas phase on the cold sample  Density functional theory calculations  DFT was employed using the PSI4 program package  
All molecules with different charge (neutral and anionic) and electronic (open-and closed-shell) states were independently investigated in the gas phase  The B3LYP exchangecorrelation functional with 6-31G basis set was employed for structural relaxation and singlepoint energy calculations  The convergence criteria were set to 10 −4 eV Å −1 for the total forces and 10 −6 eV for the total energies 
Multireference calculations  Multireference calculations were performed on the DFToptimized geometries using the QD-NEVPT2 level of theory , with three singlet roots and one triplet root included in the state-averaged calculation  A (10,10) active space (that is, 10 electrons in 10 orbitals) was used along with the def2-TZVP basis set  
Increasing either the active space size or expanding the basis set resulted in changes of about 50 meV for relative energies of the singlet and triplet states  These calculations were performed using the ORCA program package   Nucleus-independent chemical shift (NICS) calculations  Isotropic nucleus-independent chemical shift values were evaluated at the centre of each ring using the B3LYP exchangecorrelation functional with def2-TZVP basis set using the Gaussian 16 software package  
Starting materials (reagent grade) were purchased from TCI and Sigma-Aldrich and used without further purification  Reactions were carried out in flame-dried glassware and under an inert atmosphere of purified Ar using Schlenk techniques  Thin-layer chromatography (TLC) was performed on Silica Gel 60 F-254 plates (Merck) 
Column chromatography was performed on silica gel (40-60 µm)  Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker Varian Mercury 300 or Bruker Varian Inova 500 spectrometers  Mass spectrometry (MS) data were recorded in a Bruker Micro-TOF spectrometer  The synthesis of compound 6 was developed following the two-step synthetic route shown in Supplementary Fig  , which is based on the preparation of methylene-bridge polyarenes by means of Pd-catalyzed activation of benzylic C-H bonds  
Supplementary Figure | Synthetic route to obtain compound 6  The complex Pd2(dba)3 (20 mg, 0 02 mmol) was added over a deoxygenated mixture of 1,3-dibromo-2,4-dimethylbenzene (9, 100 mg, 0 38 mmol), boronic acid 10 (178 mg, 1 14 mmol), K2CO3 (314 mg, 2 28 mmol) and XPhos (35 mg, 0 08 mmol) in toluene (1:1, 10 mL), and the resulting mixture was heated at 90 °C for 2 h 
After cooling to room temperature, the solvents were evaporated under reduced pressure  The reaction crude was purified by column chromatography (SiO2; hexane:CH2Cl2 9:1) affording 11 (94 mg, 76%) as a colorless oil  The complex Pd(OAc)2 (7 mg, 0 03 mmol) was added over a deoxygenated mixture of terphenyl 11 (90 mg, 0 27 mmol), K2CO3 (114 mg, 0 83 mmol) and ligand L (26 mg, 0 06 mmol) in NMP (2 mL) 
The resulting mixture was heated at 160 °C for 4 h  After cooling to room temperature, H2O (30 mL) was added, and the mixture was extracted with EtOAc (3x15 mL)  The combined organic extracts were dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure  The reaction crude was purified by column chromatography (SiO2; hexane:CH2Cl2 9:1) affording compound 6 (8 mg, 11%) as a white solid  in AFM imaging due to their reduced adsorption height compared to the rest of the carbon atoms 
We attribute this observation to the significantly different lattice parameter of Cu(111) (2 57 Å) compared to Au(111) and Ag(111) (2 95 Å and 2 94 Å, respectively) , such that the apical carbon atoms of the pentagonal rings of 5 adsorb on the on-top atomic sites on Au(111) and Ag(111), but not on Cu(111) 
Our speculation is based on a previous study of polymers of 1 on Au(111) by Di Giovannantonio et al  , where both tilted and planar individual units of 1 were observed depending on whether the apical carbon atoms of the pentagonal rings in 1 adsorbed on the on-top or hollow sites of the surface, respectively 
Given the strong molecule-metal interaction, we found no electronic state signatures of 5 on all three metal surfaces  STM set point for AFM images: V = 0  e, Frontier orbital spectrum of 5 -1   In the anionic state, ψ2 becomes doubly occupied and ψ1 is the SOMO  Filled and empty circles denote occupied and empty orbitals, respectively 
For each panel, zero of the energy axis has been aligned to the respective highest-energy occupied orbital 



ground_truth: Lasa, Gitastrophe, and Shadoks.

prompt_front: Now, answer the following question based on the text below, only give me the answer and do not output any other words.

Question: What are the two ground states observed for indeno[1,2-a]fluorene on NaCl surfaces?

Read the following text and answer briefly.

Context 4:  (he wrote to his mother, and referred to his one-year old son Houston and the baby his wife Mabel was about to have: they were staying with his mother in the US)    That night, L  started to feel chilled as the fever came on  He never went to sleep but worked at his desk all through the night, trying to get all the information about the mosquitoes organized  By morning, he showed all the signs of a severe attack of yellow fever  The camp doctors made the diagnosis, and L  agreed to go to the yellow fever ward    L  was carried by litter out of the two-room, white pine board house in which he had lived since he and Mabel first arrived in Cuba    (In the yellow fever ward, in a separate one-room building), Lena Warner (the immune nurse who had survived the yellow fever in 1878, when she was nine, and was found in her boarded-up house by a former slave who first thought she was dead, and carried her to safety) nursed J L , recording his vitals  (I put up a link to his case record and vital signs last week  The surgeon general required that this record be made for every yellow fever patient )    (On September 25,) Lena Warner braced L's arms with all of her weight, shouting for help  Still he bolted from the bed, darting around the small frame-wood room as wildly as a trapped insect beating against glass  Two soldiers ran into the ward, pinning L to his bed, tying restraints around his wrists and elbows    Warner sponged his body with iced whiskey and water  She recorded his temperature, which had held at 104 degrees for days, on the chart beside his bed    (Warner watched him sleep ) But the quiet did not last  L's body began to lurch, and black vomit rolled from his mouth; through the bar hanging above his hospital cot  He writhed in the bed, and his skin grew deep yellow  His 104 temperature slowly fell, leveling out 99 degrees, and JL died at 8:45 p m  at the age of thirty-four "
As is obvious, there are many problems with vaccines  But, that being said, most of them usually work for a period of time to prevent the targeted diseases  The basic science behind vaccines is correct  Why do you think that within a few years (not many) of the introduction of the vaccines for them, pertussis, measles, mumps, rubella, tetanus, diphtheria, Hib disease, and chickenpox (and others) almost entirely disappeared? In the case of the routine childhood diseases, this was a bad thing, but it is a true thing 
Vaccines usually don't cause any obvious reactions  While they usually prevent the diseases, and that's why people continue to get them  With the increasing vaccination schedule, more and more are severely and permanently damaged, and it is immoral to mandate any vaccine for anyone for this reason  But it would also be immoral to prohibit vaccines for those who want them enough to take the risk 
Your article said as though it had any probative value that 90% of those who get pertussis had been vaxxed  The old DPT vaccine was MUCH more effective at preventing pertussis, but it was so dangerous (again, not to most, but to many), that developed countries replaced it with the acellular version, DTaP  From the beginning about twenty years ago, it was clear that it was not very effective and that huge numbers of vaxxed people got pertussis anyway, including my daughter who got pertussis at eight month old after having gotten three DTaPs  The pertussis vaccine continues to be very dangerous, and I do not recommend that anyone get it  It used to be a killer disease, but evolved to become much milder, to the extent that the disease is very rarely dangerous (usually only to newborns under three months old), while the vaccine is very dangerous  And they're trying to see how they can go back to the old DPT  This does not show that vaccine science has collapsed, but rather that the vaccine they developed to replace the DPT turned out to be much less effective than they first thought, while continuing to be much more dangerous than they first thought 
Your article extrapolated from that that modern medical science in general has collapsed, but that, again, is going too far  A older woman in Mexico City who is like my mother to me had a pacemaker inserted about two months ago to aid her failing heart, and it has restored her to optimism and energy, when she was despondent, weak, and close to death  I took my daughter to the dentist yesterday, who said she has three wisdom teeth coming in and that she said that the lower right one was sore  So, although I am cautious about X-rays, I made an appointment for a panoramic X-ray in a month to assess the wisdom teeth, and, if it seems appropriate, I'll take her to an oral surgeon to have one or more extracted under IV sedation, in his office, if possible (the dentist thought that it would be)  And I am confident that there will be no serious problems, but this is thanks to technology and training in modern medicine that haven't been available for that long 
I think that everyone should inform himself on all medical procedures before agreeing to anything, but I also think that he should have access to any medical procedure which is reasonable (and opinions can differ as to that) 
One problem is that you have not said how you think people should protect themselves against tetanus, bacterial meningitis, and yellow fever in the relevant cases, for example  These are diseases which healthy, well-nourished people used to die from very readily 
If most people stopped vaxxing and the mortality from these diseases rose to something like pre-vaccine levels, do you think they should just accept dying from them?
I put that in a separate paragraph because it is the crucial issue 
balinaheuchter Air Traffic Control You Tube - Colin Campbell example of - How to "Fudge a Nudge" -"Deal" or "No Deal" "Not in a month of Sundays" "No exceptions/no compromise?" -make a trade off -do an exception- everyone get's a good deal /good outcome!
Hans, you are right that we are looking at one of the biggest crimes in all history  When I read the story of that poor girl who was so healthy and is now confined to a wheelchair after getting her third Gardasil shot I could not believe that Merck could produce such a toxic vaccine and give it out to girls like it was something they absolutely had to have only to be mislead and made into cripples  Merck should be prosecuted for the damage they have done to so many girls who got the Gardasil vaccine and were physically debilitated for life  There is a place for the people who perpetrated this crime on young girls and women and it is called hell  They have destroyed people's lives and gotten away with it  My heart goes out to those who have suffered this damage for no damn good reason except to help make huge profits for Merck!
Here is the reason that the germ theory is nonsense 
1) Everyday we are bombarded with billions of germs  Presumably at least some of them are of the kind that germ theorists believe are dangerous (otherwise we would have to conclude that none of them are dangerous)  So how do we survive?
2) Let's just say that we ignore 1 and imagine that, by way of magic, none of the billions of viruses we get bombarded with are pathogenic but all those that are are tucked away somewhere  Ok  But presumably they reside in sick people right? So where are there lots of sick people? Doctor offices and hospitals! So everybody must be dying the moment they enter these places right?
3) I love this one because I have never seen anybody else ever raise it  Under the germ theory there are no negative feedbacks  This makes a stable biological system by definition impossible  The immune system is *not* a negative feedback it is the opposite  It actually reinforces our math problem because the immune system will weaken as the number of pathogens increase 
There is no way of resolving this problem without a discontinuity  A Deus ex Machina as The Almighty Pill so beautifully put it  So the germ theory is quite literally, mathematically impossible 
There is as much chance of it being true as 2+2 = 5 
There are plenty of other massive problems with germ theory such as why did things like SARS and bird flu magically disappear? Why do we have the symptoms that we do? Is our body controlling the symptoms to help fight the germs and if so, why would suppressing the symptoms with antibiotics or Tamiflu be considered a good idea? If the virus is causing the symptoms then why would it cause these kinds of things?



ground_truth: Open-shell π-diradical state and closed-shell state with a para-quinodimethane moiety.