VOLUME 79, NUMBER 7

PHYSICAL REVIEW LETTERS

18 AUGUST 1997

Hunds Rules and Spin Density Waves in Quantum Dots

M. Koskinen and M. Manninen
Department of Physics, University of Jyvskyl, P.O. Box 35, FIN-40351 Jyvskyl, Finland

S. M. Reimann
Niels Bohr Institute, DK-2100 Copenhagen, Denmark (Received 17 March 1997) Spin density functional theory is used to calculate the ground state electronic structures of circular parabolic quantum dots. We nd that such dots either have a spin conguration determined by Hunds rule or make a spin-density-wave-like state with zero total spin. The dependence of the spin-density-wave amplitudes on the density of the two-dimensional electron gas is studied. [S00319007(97)03740-X]
PACS numbers: 75.30.Fv, 71.10.Ca, 73.20.Dx

Semiconductor technology now allows the fabrication of quantum dots being so tiny that they contain only a few electrons. Usually, such dots are formed by lateral connement of a high-mobility two-dimensional electron gas (2DEG) in a semiconductor heterostructure. Their electronic properties are determined by the interplay of the external connement and the electron-electron interactions, manifesting a quantum-mechanical many-particle problem (see, e.g., Ref. [1] for exact diagonalization studies and Ref. [2] for a mean-eld approach, to mention only a few from a broad eld of research). The properties of such small dots strongly depend on the number of conned electrons, and the situation is quite similar to the different properties of the rst elements of the periodic table, why quantum dots now often are called articial atoms [3]. Recently, Tarucha et al. [4] have developed a vertically conned quantum dot, where they could experimentally show that for weak or zero magnetic elds the electronic structure of a small circular dot containing up to 20 electrons is mostly determined by the subsequent lling of shells, obeying Hunds rules as in atoms. Motivated by their experimental study, we performed spin-density functional calculations for such circular, parabolic quantum dots containing up to N 46 electrons. Complicated magnetic structures and excited states of the 2DEG have been obtained earlier in the presence of an external magnetic eld [57]. To our own surprise we found that quantum dots have a rich variety of different magnetic structures in the ground state, even without an external magnetic eld. As one would expect from the knowledge of atomic physics, Hunds rst rule dominates for the smallest sizes. However, some dots have zero total spin, but exhibit a space-dependent spin polarization, a so-called spindensity wave (SDW) [8]. At very low temperatures the electrons in the 2DEG are conned to the lowest subband, and it is thus sufcient to consider them as being bound laterally in the 0031-9007 97 79(7) 1389(4)$10.00

x-y plane. For such small dots as studied here, we then make the frequently used [1,2] approximation that the external potential is harmonic, V m v 2 x 2 1 y 2 2. In such a parabolic dot the single-particle electron levels form a pronounced gross-shell structure, the magic shells corresponding to electron numbers 2, 6, 12, 20, 30, . . . . The exact degeneracy of the shells of the 2D oscillator, however, is reduced by the electron-electron interactions. The situation in the case of open shells is analogous to that in atoms. For example, if a shell is half lled, the spins align according to Hunds rules. This causes the empty states with opposite spin to be higher in energy and removes the degeneracy of the Fermi level. In the case of atoms the ionization potential as a function of the atomic number has maxima at half-lled p shells. The experiments of Tarucha et al. [4] for parabolic quantum dots show a quite similar behavior: A halflled shell shows a maximum in the addition energies as a manifestation of Hunds rst rule. For the electronic structure calculations for N electrons in the parabolic dot, we apply density functional theory [9,10] and treat the exchange-correlation part of the electron-electron interactions in the local spin-density [11] approximation. To be more specic, we solve the singleparticle Kohn-Sham [10] equations h2 2 s = 1 Veff x ci,s x ei,s ci,s x , (1) 2 2m x where x x, y and the index s accounts for the spin (" or #). The effective Kohn-Sham potential consists of the external harmonic connement, the Hartree potential of the electrons, and the functional derivative of the local exchange-correlation energy Z dx n x exc n x , z x , (2) Exc where n is the electron density and z n" 2 n# n the spin polarization. For the exchange-correlation energy of the homogeneous 2D electron gas, we use the parametrized form of Tanatar and Ceperley [12] for nonpolarized 1997 The American Physical Society 1389

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PHYSICAL REVIEW LETTERS

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(z 0) and ferromagnetic (z 1) cases. For intermediate polarizations, following the work of von Barth and Hedin [11] as well as Perdew and Zunger [13], which is frequently used for electronic structure calculations in 3D systems, one can write exc n, z exc n, 0 1 f z exc n, 1 2 exc n, 0 . (3)

TABLE I. Total spin S of the ground states and some lowenergy spin isomers for rs 1.51aB . States with a S 0 spindensity wave are labeled SDW, whereas nonzero total spins according to Hunds rules are labeled with H. Number of electrons 2 4 6 8 10 12 14 16 Ground state 0 1 0 1 1 0 1 2 H H H H H 0 SDW 0 SDW 23.0 4.62 Excited state(s) DE (mRy*)

The polarization dependence f z in 2D [14] is then f z 11z

3 2

1 12z 23 2 2 2

3 2

22

(4)

In order to obtain the electron densities which minimize the total energy functional E n" , n# , the Kohn-Sham equations are solved self-consistently. To avoid any symmetry restrictions for the wave functions, we use a plane-wave basis. To nd the ground state of all the possible spin congurations, the iterative solution of the Kohn-Sham equations was started with different forms and depths of the initial potential for the spin up and down densities [15]. This assures that one is not trapped in a local minimum, but with a high probability can separate the electronic ground-state conguration from the lowest excited states. The results will be given in effective atomic units with h 2 4pe0 e m e2 , Ry m e4 2h2 4pe0 e 2 and aB where m is the effective mass and e the dielectric constant. The results can then be scaled to the actual values for typical semiconductor materials. The calculations are done for different values of the density parameter rs , which approximately correspond to 2 the average particle density in the dot, n0 1 prs . For the external parabolic connement, which actually determines the average particle density, we then use v 2 p 3 e2 4pe0 em rs N . We have rst calculated ground-state and isomeric electronic structures for quantum dots corresponding to the equilibrium density of the two-dimensional electron gas with rs 1.51aB . The results for dots with even electron numbers N are summarized [16] in Table I. Dots with 2, 6, 12, 20, and 30 electrons correspond to magic congurations of a 2D harmonic well and have a particularly large Fermi gap. Consequently, the system is fully paramagnetic and the ground-state total spin in all these cases is zero. For nonclosed shells, however, in most of the cases the total spin [17] is determined by Hunds rule, which maximizes the spin for orbital degeneracy. From Table I we see that dots with N 4, 8, 10, 14, 18, 22, 28, and 32 electrons have total spin S 1 in the ground state, whereas for dots with 16 and 26 electrons ground states with a total spin S 2 were found. For larger dots we found up to three different spin isomers, being little higher in energy than the groundstate conguration. As an example, we show in the rst row of Fig. 1 the spin down and spin up ground-state 1390

18 20 22 24 26 28 30 32 34

1 0 1 0 2

H H SDW H

0 1 0 0 0 2 0 0 0

SDW H SDW SDW SDW H SDW SDW SDW

18.1 20.2 20.7 11.05 9.06 0.72 2.75 6.46 1.98 7.06 0.73

1H 0 1H 0 SDW

0 SDW 2H

FIG. 1. Spin down and spin up densities n # , n" and normalized polarization z x, y for the ground state (rst row) and excited states (lower rows) for a dot with N 16 electrons and rs 1.51aB . The maximum amplitude for the polarization corresponds to z x, y 0.23.

VOLUME 79, NUMBER 7

PHYSICAL REVIEW LETTERS

18 AUGUST 1997

densities for N 16, together with the normalized po larization z n" 2 n# n0 . In this case the total spin is S 2. It is intriguing to see that z shows a pronounced radial oscillation, which means that the excess spin is not homogeneously distributed over the whole dot regime. This effect was also seen for other sizes N when the ground state had nonzero total spin. It reminds one of the spin inversion states found by Gudmundsson et al. [6] for nite magnetic elds. 1.51aB the total For many of the excited states at rs spin is zero. A priori one would in these cases expect that the system is fully unpolarized. But now looking again at Fig. 1, where the three lower rows show the densities and polarizations of the three different spin isomers for N 16, we see that the electronic structure is more complicated. Both the second and fourth rows of Fig. 1 show isomeric S 0 states, being slightly higher in energy than the ground state (see Table I). Their space-dependent spin polarization shows apparent spatial oscillations, which remind one of the phenomenon of spin-density waves [8] in the bulk. The spin-density-wave-like states in the nite 2D system (which in the following are called SDW states) associate a certain preferred spin direction with a given spatial region in the dot. Studying these effects further, the next surprise is that in larger dots this rather peculiar electronic structure with total spin S 0 gets even lower in energy than the Hund state. For N 24 and N 34, the ground state has spin zero, but is associated with a SDW state which has a lower energy than the uniform state. (Its shape is similar to the one shown in Fig. 3 below for 5.0aB .) The general possibility of such ground-state rs congurations with uniform or nearly uniform electron density, but a nonuniform density of spin magnetization, was rst discussed by Overhauser [8]. He stated that the nonmagnetic state must become unstable with respect to SDW formation at low densities, whereas at higher, metallic densities, it seems unlikely that the SDW state is of enhanced stability. The energy balance, however, is very delicate. Overhauser pointed out [8] that when the SDW states are stable, they are energetically only slightly lower than the nonmagnetic state. On the basis of the results discussed above it is now interesting to study how the SDW states depend on the density of the two-dimensional electron gas. We thus calculated for selected electron numbers the ground state as a function of the strength v of the conning harmonic potential, corresponding to rs values from 0.25aB to 5.0aB . Figure 2 shows the maximum amplitude of the nor malized polarization z as a function of rs for dots with N 24, 34, and 46 electrons, where the SDW was found to be the ground state. It can be clearly seen that, depending on the size N, there is a critical value of rs , where the SDW sets in, and then rises its amplitude with increasing rs . Note, however, that the N dependence of the critical value of

FIG. 2. Maximum amplitudes of z x, y of the ground-state SDW for N 24, 34, and 46 as a function of rs .

rs does not generally follow the trend suggested from this gure: For some N , 46, the SDW sets in at a higher critical value of rs , but with a comparable amplitude. From our calculations we nd that even in magic congurations, which are fully paramagnetic with total spin zero at low rs values, for sufciently large rs the SDW formation sets in. In the case of the lled shells N 12, 20, and 30 a SDW state was obtained for very large rs * 5aB . Increasing rs still further, this SDW state gets more pronounced, in a similar way than the examples with N 24, 34, and 46 discussed above. Finally, we note that the occurrence of a SDW is related to a change in the pattern of the single-particle levels. As an example, we show in the bottom of Fig. 3 the Kohn-Sham single-particle spectra of N 34 at a 5.0aB , both for the grounddensity corresponding to rs state SDW with S 0 and the excited state with total spin S 2, being 1.9 mRy higher in energy. The third spectrum shows the result of a LDA calculation for the unpolarized case, which gives a 2.13 mRy higher energy than the SDW state. Note that for a SDW, there is always one pair of degenerate spin up and spin down orbitals, and the Fermi gap of the SDW state is much higher than in the S 2 case or within LDA. In quite a similar way to the spontaneous shape deformations of nuclei with nonclosed shells [18], the SDW opens a large energy gap at the Fermi surface, leading to a more stabilized electronic structure in the dot. In conclusion, we have found that in nite quantum dots a static spin-density-wave-like state occurs even at rather high densities of the two-dimensional electron gas. For many open-shell systems we found that the SDW state with zero spin has a higher energy than the ground state. In other cases the SDW is the ground state. Also for nonzero total spin a strong spatial dependence of the spin polarization was found. The amplitude of the SDW strongly depends on the size of the Fermi gap: The 1391

VOLUME 79, NUMBER 7

PHYSICAL REVIEW LETTERS

18 AUGUST 1997

FIG. 3. Upper part: Polarization z x, y for N 34 at rs 5aB . Left: Ground state with S 0. Right: Excited state with S 2. The scales are the same as in Fig. 1 above. Lower part: Single-particle spectra for N 34 at the same density rs 5aB . The numbers in the spectra indicate the degeneracies of the occupied single-particle states. The shorter lines indicate the lowest unoccupied states. Left: Hunds case with S 2. Middle: SDW ground state with S 0. Right: LDA result, unpolarized. The total width of the spectrum is about 73.5 mRy .

inset of the SDW-like state for the magic congurations occurs at much higher rs values than for nonclosed shells. Recent calculations have shown that the SDW-like states are rather stable against distortions of the external connement. In a real quantum dot, the deformations of the effective connement (caused, for example, by quantum point contacts) will thus lead to a pinning of the polarization. Rather peculiar properties of such quantum dots could be expected. We would like to thank J. Helgesson, P. E. Lindelof, and B. R. Mottelson for helpful discussions. This work was partially nanced by the Studienstiftung des deutschen Volkes, the BASF AG, the Academy of Finland, and CNAST. S. M. R. thanks the University of Jyvskyl for its hospitality.

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