PHYSICAL REVIEW B 67, 113408 2003

Control of substituent ligand over current through molecular devices: An ab initio molecular orbital theory
H. Chen,1,2 J. Q. Lu,1,3 J. Wu,1,3 R. Note,1 H. Mizuseki,1 and Y. Kawazoe1
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan Physics Department, Fudan University, Shanghai 200433, Peoples Republic of China 3 Centre for Advanced Study, Tsinghua University, Beijing 100084, Peoples Republic of China Received 6 May 2002; published 31 March 2003
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We explain the order of current curves of the ligand-substituent benzene-derivative devices by an ab initio molecular orbital theory on the basis of the rst-principles density functional theory and the nonequilibrium Green function technique. The results of our calculation show the control of the substituent ligand over electronic transport through the molecular device. Contrary to the Huckel tight-binding result, we nd that both the LUMO and LUMO 1 of the extended molecule the benzene derivative pluses one gold atom on each side are localized states, which have no contribution to transport. It is straightforward to extend the full molecular orbital theory to any electrode-molecule-electrode system. DOI: 10.1103/PhysRevB.67.113408 PACS number s : 73.23. b, 85.65. h, 31.15.Ar

The signicant advances in fabrication and investigation of molecular electronic wires, diodes, and switches indicate that the molecular electronic device is a potential successor to silicon-based integrated circuits.13 The early prediction proposed by Aviram and Ratner4 in the mid-1970s has come true. There are inherent advantages in the use of molecular devices. The devices are of nanoscale size with high integration density and can be fabricated in a self-assembled manner. During the design of the molecular electronic logical devices, the main challenge is to control the electronic ow through the molecule, which is connected to the bulk electrodes on both sides. After the successful experimental work on current through a nanoscale object, for example a single C60 molecule,5 single/double Xe atom wires,6 and a single benzene molecule,7 which acts as the core of the molecular device, many theoretical investigations have been done on this subject.8 13 Recently, Vilan et al.14 measured electronic current through the Au/n-GaAs diode covered by benzene derivatives. In their experiment, molecular control over electronic transport of the diode was realized. The current-voltage I-V curves of the metal-semiconductor-molecule devices are dominated by a ligand bonded to the benzene. The different ligands are chosen as the hydrogen-substituents in the experiment from the acceptor substituents -CF3 and -CN to the donor substituents -CH3 and -OCH3 , as well as the pure benzene without any substituents. The I-V characteristics of three-benzene-ring molecule, with ligand -NH2 and -NO2 bonded to the middle benzene, were measured early by Chen et al.15 Due to motivation from the experiments, we investigate the transport behavior of different benzene derivatives, which are dressed by gold electrodes on both sides, to explore the control of the substituent ligand over electronic transport of the gold-molecule-gold sandwich system. In our calculation, the organic molecule is described by the Roothaan equation, and the transport behavior of the molecular device is dominated by the molecular levels and molecular orbitals MOs . The molecular orbitals are expressed as a linear combination of the atomic basis functions, which are
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especially suitable for the problem with contacts.13,16,17 The inuence of the substituent ligand on the electronic coupling in a molecular complex was investigated in the context of electron transfer through a molecule early in 1991.17 The molecular theory was used to interprete STM and AFM experiments and to calculate the conductance of many molecules.18 In our model, we extended the benzene-derivative molecule to include one sulfur atom and one gold atom on both sides as an extended molecule later in this article we simply call it molecule in order to renormalize the molecular levels and orbitals, which are modied by two semi-innite electrodes. After the geometry optimization of the molecule the AuS bond length is 2.37 and the angle CSAu is 102.8), the molecular energy levels and orbitals are calculated by the standard quantum chemistry program, Gaussian 98.19 In the calculation, both the Becke-3 hybrid exchange functional20 and the Perdew-Wang-91 generalized-gradient approximation GGA 21 are used with the Los Alamos National Laboratory basis set.22 The basis set includes initial effective core potentials ECP which are specially designed for the fth-row CsAu atoms with considering Darwin relativistic effect. A self-consistent calculation is included in the method. Then the coupling between the gold atom in the extended molecule and three gold atoms in 111 direction in electrodes considering only the nearest neighbor interaction is calculated on the same footing. The large cluster of gold atoms costs much more computer time. As the rst order approximation we consider the rst neighbor interaction between the gold atoms in the electrode, meanwhile we calculate all the interaction between the organic molecule and the gold atom at the interface. A large cluster of gold atoms will not change our results, our test calculation shows four gold atoms are enough. There are several problem in dispute now. The rst one is the position of Fermi level, that has strong effect on the property of electronic transport. Some authors choose Fermi level near HOMO level, while others near the middle of HOMO-LUMO gap HLG , and even near LUMO. The extended molecule is dressed by the bulk electrodes, and the
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PHYSICAL REVIEW B 67, 113408 2003

FIG. 1. Color The current behavior of -CH3 and -CF3 due to the contribution from s-, sp- and spd-model of the gold Green function.

FIG. 2. Color I-V characteristics of benzene derivatives with substituent ligands: -OCH3 , -OH, -CH3 , -H, -CF3 , -CN, -NO2 . The inset shows a benzene derivative attached by four gold atoms in the electrode on each side.

Fermi level is decided by electrodes themselves. We choose the work function of Au 111 in Ref. 23 as Fermi level: 5.31 eV. 13 The interaction between the gold atom at interface and the benzene molecule elevates HOMO and LUMO, especially the latter, and enlarges HLG of the extended molecule. The Fermi level is inside the HOMO-LUMO gap of the extended molecule for many benzene derivatives. Then the gold can be used as electrodes in many benzene derivative devices, as shown in the experiment.14 The second problem is the choice of the Green function of the gold electrode. The typical and simple approximation for the gold Green function is a diagonal matrix with each ele-

ment equal to (- i) times the local density of states LDOS , 0.072 i/eV-atom which is obtained from Ref. 24. (g s 0.0426 i/eV-atom for p orbital, and for s orbital, g p 0.1286 i/eV-atom and g e g 0.0492 i/eV-atom g t2g for d orbital, respectively . Most authors adopted s model, some spd model. From Fig. 1 one can see that s model gives main contribution for the low bias; but for the whole range of bias sp and spd models give a better current behavior according to the experiment.7 In Figs. 2 and 3 we adopt sp model. The electronic transmission function of the whole system

FIG. 3. Color Transmission function black curve and density of states red as functions of the injection energy of electron of the benzene derivative attached by ligand from top to bottom: -OCH3 , -H, and -CN. The straight-lines indicate the position of Fermi level red line , and the range of current integration E f 2.5 eV green lines . The short bars present the energy levels of the extended molecule. The characters H and L represent HOMO and LUMO, respectively. 113408-2

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PHYSICAL REVIEW B 67, 113408 2003

is evaluated by using the nonequilibrium Green function technique:25,11 T Tr( 1 G M 2 G ), where Tr, the trace, is M over all the orbitals of the extended molecule, and i , the spectral density, describes the coupling at contact i in terms of the self-energy i i( i i ). In the retarded Green function of the molecule system, G M , the semi-innite electrode is taken into account through self-energies 1 and 2 : 1 , with the self-energy for elecG M (ES F 1 2) trode i, i M M i g i M iM (i 1,2) and the coupling matrix M ES F. The molecular orbital matrix C and the diagonal matrix of the molecular orbital energy are obtained from the Roothaan equation FC SC . The Fock matrix involves the core Hamiltonian and the two-electron Coulomb interaction. In this way the Green function is constructed due to all the knowledge of the molecular levels and orbitals. The conductance is proportional to the transmission function G (2e 2 /h)T, with the quantum conductance 2e 2 /h 1/12.9k . Then current can be obtained from integration dET(E,V) f (E of transmission function I (2e/h) f (E 1) 2 ) with the electrochemical potentials in 1 two contacts 1 E f 2 eV and 2 E f 1 eV, and the 2 Fermi distribution function f (E) 1/(e E 1). Because k B T 26 meV at the room temperature, the temperature effect is relatively insignicant on eV energy scale in our cal) can be treated as the step function calation and f (E E). 9 ( Figure 2 shows the current-bias characteristics of the benzene derivative devices dressed by gold electrodes on both sides. The result presents control over the current by the substituent ligand group attached to the benzene. Current curve of the pure benzene, which is in the middle, acts as a boundary. Current curves of benzene derivatives with donor ligand, -OCH3 , -OH, -CH3 , are on the left side, while the ones with acceptor ligand, -CF3 , -CN, -NO2 , on the right side. The order of the current curves is different from that of the benzene derivatives which are absorbed on GaAs semiconductor,14 because that is a totally different device. Our result can be explained by the molecular orbital theory and transmission function curves. Figure 3 presents the mechanism that the transmission function determines the current behavior in Fig. 2. Three typical benzene derivatives, -OCH3 the donor dopant , -H for the pure benzene , and -CN the acceptor dopant , are chosen as examples. The details of the transport behavior are shown by the transmission function black curve and density of state red curve as functions of the injection energy of electron. The peaks of density of states DOS indicate not only the positions of the renormalized molecular levels of the extended states, but also the broadening of the molecule levels due to the presence of the semi-innite electrodes and bias. The straight-lines indicate the position of Fermi level E f red line , and the integration range green lines , E f 2.5 eV, for the maximum bias V 5 eV in Fig. 2. The energy levels of the extended molecule are represented by the short bars near the energy axes. The characters H and L represent HOMO and LUMO, respectively. Contrary to the

Huckel tight-binding result,11 LUMO and LUMO 1 for all the seven benzene derivatives in Fig. 2 are localized states, which have no contribution to transport. The main contribution to current comes from HOMO-n to HOMO level for bias V 5 eV, where n 5 for -OCH3 , n 4 for -H, and n 2 for -CN. It can be seen from the gure that the shortest distance between E f and the descending branch of the transmission function exists in the gure of -OCH3 , which dominates the largest current and the smallest threshold value of current in comparison to the pure benzene and the one with ligand -CN. In fact, the current of the molecular device with -OCH3 is the largest one among all the seven benzene derivatives in Fig. 2. The distance between E f and the descending branch of transmission function is the key point to determine the order of current curves in Fig. 2. The deep drop in transmission function for benzene derivatives with -OCH3 and -OH not shown in Fig. 3 leads a current plateau in Fig. 2. In summary, we use a full molecular orbital theory to study the transport behavior through metal/benzenederivative/metal sandwich system by an ab initio density functional theory and the nonequilibrium Green function method. In the theory, the precise position of every atom in the molecular device and all the information about the molecular orbitals and levels are considered carefully. The calculation results explain the magnitude value and order of current. The theory may provide an effective way to design the electronic molecular devices with desired properties. The density-functional theory DFT in the local dentity approximation LDA or the generalized gradient approximation GGA , which has been very successful for computation of the ground-state properties, underestimates HOMO-LUMO gap compared to experiments.26 28 The unlled levels, like LUMO and LUMO n, may be too low in the DFT calculation. Fortunately, higher LUMO and LUMO n will not affect our conclusion, since they have no contribution to conductance according to our results Fig. 3 . So our conclusion, the order of the current curves, is still valid in the better approximations. In case the value of the HOMO-LUMO gaps is critical, the better theory, the GW aproximation, may be applied, which may greatly increase the computational load.
ACKNOWLEDGMENTS

The authors would like to express their sincere thanks to the support from the staff at the Center for Computational Materials Science of IMR-Tohoku University for the use of the SR8000 G1/64 supercomputer facilities. This study is performed through Special Coordination Funds of the Ministry of Education, Culture, Sports, Science and Technology of the Japanese Government, and partly supported by the Natural Science Foundation of China NSFC under Project 19874012, the Ministry of Education of China, and the National Key Program of Basic Research Development of China Grant No. G2000067107 .

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