text:
# Effect of the Surface on the Electron Quantum Size Levels and Electron 𝑔-Factor in Spherical Semiconductor Nanocrystals

## I Introduction

The modern technique of nanocrystal growth has created high optical quality nanocrystals with narrow size distributionbrus ; Murray  that can be also chemically doped.Sionest  This allows one to study the level structure of the nanocrystals using interband optical spectroscopy,josa ; norris ; Klimov  tunneling spectroscopy,banin ; millo  and the far–infrared intraband spectroscopy.Sionest ; shim  Important additional information about the origin of these levels and their symmetry could be obtained by using optical magnetospectroscopy of the intraband and interband transitions and tunnelling magnetospectroscopy, as was done many years ago in the case of atoms, hydrogenlike shallow defects and excitons. There is the other group of experiments, such as magneto circular dichroism,kuno  spin–flip Raman scattering,sirenko  time dependent Faraday rotation,gupta ; gupta02  EPR and ODMR measurements,nozik1 ; nozik2 ; lifshitz  and magneto-photoluminescence,Efrosprb96  where the magnetic field is an essential component of the experimental technique. Inrepretation of all these experiments requires the knowledge of electron and hole energy spectra in magnetic fields.

A wide class of semiconductor materials can be prepared in nanocrystal form. In most cases they have a spherical shape and can be bare semiconductor nanocrystals or onion type heterostructure nanocrystals composed of an inner semiconductor core coated with several spherical shells of different semiconductors.alivisatos ; weller ; bawendi  Technology allows one to vary the radius of the nanocrystal core from 10–40 Å in a controlled manner. The energy spectra of the NCs are formed by the discrete quantum size levels (QSLs). The QSLs of the confined electrons in the conduction band are characterized by the value of the orbital momentum $`l`$ and the total angular momentum $`j=l\pm 1/2`$, similar to the bound electron states in atomsbethe . In a zero magnetic field, the levels are degenerate with respect to the projection of the total momentum $`j`$.

The spectra of the nanocrystals in an external magnetic field $`H`$ is well described as an atomic Zeeman effect. A diamagnetic $`H^2`$ contribution to the spectra could be neglected because the nanocrystal radius, $`a`$, is considerably smaller than the magnetic length, $`L=\sqrt{e\mathrm{}/cH}`$, where $`e`$ is the absolute value of a free electron charge, $`c`$ is the speed of light. In a reasonable magnetic field $`H<10`$ T the diamagnetic contribution to the QSLs $`(a/L)^41`$. However, the effect of the external magnetic field on the electron QSLs depends on the zero field spin-orbit splitting, $`\mathrm{\Delta }_c`$, of the levels with different $`j=l\pm 1/2`$ (One can find a description of the similar effect for atoms in Ref. bethe, ). If $`\mathrm{\Delta }_c`$ is larger than the Zeeman energy, the weak magnetic field splits the electron levels:

$$\mathrm{\Delta }E_j^\pm =\mu _Bg_j^\pm mH,m=j,j+1,\mathrm{},j,$$
(1)
where $`\mu _B=e\mathrm{}/2m_0c`$ is the Bohr magneton, $`m_0`$ is the free electron mass, $`m`$ is the projection of the total momentum on the magnetic filed direction and $`g_j^\pm `$ is the effective $`g`$-factor of the corresponding state, that is an analog of the Land$`\stackrel{´}{e}`$factor for atoms. If $`\mathrm{\Delta }_c`$ is small, the Zeeman splitting can be described as the sum of the spin and orbital contributions:

$$\mathrm{\Delta }E_l=\mu _Bg_ss_zH+\mu _Bg_ll_zH,$$
(2)
where $`s_z=\pm 1/2`$ and $`l_z=l,l+1,\mathrm{},l`$ are the electron spin and angular momentum projections on a magnetic field direction correspondingly, and $`g_s`$ and $`g_l`$ are the spin and orbital g-factors of the electron in the corresponding state. In bare nanocrystals made of semiconductors with a simple parabolic conduction band $`g_s`$ is equal to the bulk electron effective $`g`$–factor $`g_c`$ and $`g_l=m_0/m_c`$, where $`m_c`$ is the bulk electron effective mass.

Spin–flip Raman scattering studies of CdS nanocrystals,sirenko  however, have demonstrated the dependence of the ground 1S electron state $`g_s`$ on the excitation energy, and thus on the energy of the electron state. The variation of $`g_s`$ with energy can be connected with the energy dependence of the bulk electron $`g`$–factor.sirenko  The eight band Kane model, that is used to describe the electron energy spectra in most direct gap semiconductors, gives the following dependence of the electron $`g`$–factor $`g_c(E)`$ on its energy, $`E`$:roth ; weisbuch

$$g_c(E)=g^{}\frac{2E_p}{3}\frac{\mathrm{\Delta }}{(E_g+E)(E_g+\mathrm{\Delta }+E)}.$$
(3)
Here $`E_g`$ is the band gap energy, $`\mathrm{\Delta }`$ is the spin–orbit splitting of the top of the valence band, $`E_p`$ is the energetic Kane parameter, and $`g^{}=g_0+\mathrm{\Delta }g`$, where $`g_0=2`$ is the free electron $`g`$–factor and $`|\mathrm{\Delta }g|1`$ is the contribution of remote bands to the bulk electron $`g`$ factor. The second term in Eq. (3) describes the negative contribution of the valence band (with $`\mathrm{\Delta }>0`$) into the electron $`g`$-factor. It decreases with increasing the energy of QSLs caused by the reduction of the nanocrystals size. Thus, the energy dependence of $`g_c(E)`$ in Eq. (3) is conducive to the size dependence of $`g_s`$ in Eq. (2), that has been measured recently in bare and core-shell CdSe nanocrystals.gupta02

The size dependence of $`g_s`$ for the ground 1S electron state in the spherical heterostructure has been calculated in Ref. kiselev,  within the eight band Kane model. It has been shown that in a spherical heterostructure formed by two semiconductors, $`A`$ and $`B`$, $`g_s`$ is the sum of the weighted volume contributions of each material and the interface contributions: $`g_s=\overline{g_s(A)}+\overline{g_s(B)}+g_{AB}`$. The interface term, $`g_{AB}`$, is proportional to the square of the conduction band component of the wave function, $`f_c`$, at the $`A/B`$ heterointerface. This calculation shows clearly that $`g_s`$ is very sensitive to the value of the wave function at the heterointerface and to its leakage under the barrier and thus to the boundary conditions (BCs) imposed on the wave function at the heterointerface. In Ref. kiselev,  the size dependence of the electron g-factor is calculated using standard BCs that assumes a continuity of $`f_c`$ at the interface. This leads to the vanishing of the interface term, $`g_{AB}`$, in the bare semiconductor nanocrystals, that are modeled by the infinite potential barrier in the layer $`B`$ because the standard BC at the surface in this case is $`f_c=0`$.

However, the standard BCs are not always justified even for infinite potential barriers (see for example Refs. brag99, ; bc, ). In general, the wave function $`f_c`$ does not vanish at the surface of bare semiconductor nanocrystals and satisfies the general boundary conditions that are the characteristics of the particular surface.brag99 ; bc  The effect of a semiconductor surface on the light absorption in indirect band semiconductor nanocrystals has been studied in Ref. brag99,  and was found to be significant.

In this paper we study the effect of the general boundary conditions on the QSLs of an electron in zero and weak external magnetic fields. We show that there is an additional surface–induced spin–orbit term for the electron states whose magnitude is proportional to $`\mathrm{\Delta }|f_c(a)|^2a^3`$. This surface–induced spin–orbit interaction leads the additional magnetic moment of the electrons in an external magnetic field in analogy with the additional relativistic magnetic moment of the electrons in atoms.abragam ; margenau  This is conducive to the nonzero surface contribution to the electron $`g`$ factor that controls the linear Zeeman splitting of the QSLs. The fitting of the experimental size dependence of the electron $`g`$ factor in the ground stategupta02  has allowed us to determine the appropriate parameter of the general boundary conditions for bare CdSe nanocrystals. The spectra of excited electron states has been considered in the two limits of the relation between the zero field spin–orbit splitting and the electron energy in magnetic field similar to consideration conducted for atoms.bethe

The paper is organized in the following way: In Sec. II we describe the eight–band Hamiltonians that include the external magnetic field effects. In Sec. III we derive the general boundary conditions for the conduction band component of the envelope function at the abrupt surface (see Sec. III.1) and analyze the surface effect on the electron QSLs in a zero magnetic field (see Sec. III.2). The effect of the weak external magnetic field on the electron QSLs is considered in Sec. IV. The size dependence of the electron ground state $`g`$ factor in bare CdSe nanocrystals has been calculated and the value of the surface boundary parameter has been determined by fitting experimental data in Sec. IV.2. The symmetry of the electron excited states in an external magnetic field is studied in the low and strong magnetic field regimes (see Sec. IV.3). The results are summarized and discussed in Sec. V.

## II Effect of a weak magnetic field on the QSLs within the eight–band model: perturbation approach

### II.1 The eight band model

The energy band structure of the cubic semiconductors near the center of the first Brillouin zone can be well described within the eight–band $`𝐤𝐩`$ model.pb ; bir ; ivchenko  In the homogenous semiconductor, the full wave function can be presented as the expansion:bir

$`\mathrm{\Phi }(𝒓)`$ $`=`$ $`{\displaystyle \underset{\mu =\pm 1/2}{}}\mathrm{\Psi }_\mu ^c(𝒓)|Su_\mu +`$ (4)
$`{\displaystyle \underset{\mu =\pm 1/2}{}}{\displaystyle \underset{\alpha =x,z,z}{}}\mathrm{\Psi }_{\alpha \mu }^v(𝒓)|R_\alpha u_\mu ,`$
where $`u_{1/2}`$ and $`u_{1/2}`$ are the eigenfunctions of the spin operator $`\widehat{𝑺}=1/2\widehat{𝝈}`$, where $`\widehat{𝝈}=\{\widehat{\sigma }_x,\widehat{\sigma }_y,\widehat{\sigma }_z\}`$ are the Pauli matrices, $`|S`$ is the Bloch function of the conduction band edge at the $`\mathrm{\Gamma }`$–point of Brilluoin zone representing the eigenfunction of internal momentum $`I=0`$, and $`|R_x=|X`$, $`|R_y=|Y`$, $`|R_z=|Z`$ are the Bloch functions of the valence band edge at the $`\mathrm{\Gamma }`$–point of Brillouin zone. The combination of these functions: $`1/\sqrt{2}(|R_x\pm i|R_y)`$ and $`|R_z`$ are the eigenfunctions of the internal momentum $`I=1`$ with projections $`\pm 1`$ and $`0`$ on the $`z`$ axis respectively (see Refs. bir, ; lut, ). The smooth functions $`\mathrm{\Psi }_{\pm 1/2}^c(𝒓)`$ are the components of the conduction band spinor envelope function $`\mathrm{\Psi }^c=\left(\begin{array}{c}\mathrm{\Psi }_{1/2}^c\\ \mathrm{\Psi }_{1/2}^c\end{array}\right)`$, and $`\mathrm{\Psi }_{x\pm 1/2}^v(𝒓)`$, $`\mathrm{\Psi }_{y\pm 1/2}^v(𝒓)`$, $`\mathrm{\Psi }_{z\pm 1/2}^v(𝒓)`$ are the $`x,y,z`$ components of the valence band spinor envelope vector $`𝚿^𝐯=\left(\begin{array}{c}𝚿_{}^{𝐯}{}_{1/2}{}^{}\\ 𝚿_{}^{𝐯}{}_{1/2}{}^{}\end{array}\right)=\{\left(\begin{array}{c}\mathrm{\Psi }_{x\mathrm{\hspace{0.17em}1}/2}^v\\ \mathrm{\Psi }_{x1/2}^v\end{array}\right),\left(\begin{array}{c}\mathrm{\Psi }_{y\mathrm{\hspace{0.17em}1}/2}^v\\ \mathrm{\Psi }_{y1/2}^v\end{array}\right),\left(\begin{array}{c}\mathrm{\Psi }_{z\mathrm{\hspace{0.17em}1}/2}^v\\ \mathrm{\Psi }_{z1/2}^c\end{array}\right)\}`$. In the presence of external magnetic field the eight–component envelope function $`\mathrm{\Psi }(𝒓)\{\mathrm{\Psi }^c(𝒓),𝚿^v(𝒓)\}`$ is the solution of the Schrödinger equationpb

$`\widehat{H}(\widehat{𝒌})\left(\begin{array}{c}\mathrm{\Psi }^c\\ 𝚿^v\end{array}\right)=E\left(\begin{array}{c}\mathrm{\Psi }^c\\ 𝚿^v\end{array}\right),`$ (9)
$`\widehat{H}(\widehat{𝒌})=\left(\begin{array}{cc}\widehat{H}^c(\widehat{𝒌})& i\mathrm{}P\widehat{U}_2\widehat{𝒌}\\ i\mathrm{}P\widehat{U}_2\widehat{𝒌}& \widehat{H}^v(\widehat{𝒌})\end{array}\right).`$ (12)
Here, the energy $`E`$ is measured from the bottom of the conduction band, $`\widehat{𝒌}={\displaystyle \frac{1}{\mathrm{}}}\left(\widehat{𝒑}+{\displaystyle \frac{e}{c}}𝑨\right)`$, where $`\widehat{𝒑}=i\mathrm{}\mathbf{}`$ is the momentum operator and $`𝑨=(1/2)[𝑯\times 𝒓]`$ is the vector potential of the magnetic field. The $`2\times 2`$ unit matrix, $`\widehat{U}_2`$, and the Pauli matrices, $`\sigma _x`$, $`\sigma _y`$ and $`\sigma _z`$, are acting on the spinor components of the wave functions ($`\mu =\pm 1/2`$). $`P=iS|\widehat{p}_z|Z/m_0`$ is the Kane matrix element describing the coupling of the conduction and valence bands (The Kane energy parameter: $`E_p=2m_0P^2`$, was introduced in Eq. (3), respectively). The off-diagonal matrix element in Eq. (12) acts on the $`𝚿^v`$ as a scalar product $`\widehat{𝒌}𝚿^v\widehat{k}_x\mathrm{\Psi }_x^v+\widehat{k}_y\mathrm{\Psi }_y^v+\widehat{k}_z\mathrm{\Psi }_z^v`$. The conduction band part of the Hamiltonian, $`\widehat{H}^c`$, acting on the spinor function $`\mathrm{\Psi }^c`$ has the form:

$$\widehat{H}^c(\widehat{𝒌})=\frac{\alpha \mathrm{}^2}{2m_0}\widehat{U}_2\widehat{k}^2+\frac{1}{2}g^{}\mu _B(\widehat{𝝈}𝑯),$$
(13)
where $`g^{}`$ is defined in Eq. (3), and $`\alpha `$ takes into account the contribution of remote bands to the energy–dependent electron effective mass, $`m_c(E)`$. In cubic and zinc-blende semiconductors this dependence has the following form:

$`{\displaystyle \frac{m_0}{m_c(E)}}=\alpha +{\displaystyle \frac{E_p}{3}}\left[{\displaystyle \frac{2}{E_g+E}}+{\displaystyle \frac{1}{E_g+E+\mathrm{\Delta }}}\right].`$ (14)
In this paper we focus only on the electron QSLs with energies $`0<E<Eg`$. This allows us to neglect hereafter the $`k^2`$ terms in the valence band part of the Hamiltonian, $`\widehat{H}^v`$, and to present it in the spherical approximation as:bir ; lut

$`\widehat{H}^v(\widehat{𝒌})`$ $`=`$ $`\left(E_g+{\displaystyle \frac{1}{3}}\mathrm{\Delta }+(1+3\kappa )(\widehat{𝑰}𝑯)\right)\widehat{U}_2`$ (15)
$`+`$ $`{\displaystyle \frac{1}{3}}\mathrm{\Delta }(\widehat{𝑰}\widehat{𝝈})+{\displaystyle \frac{1}{2}}\mu _Bg_0(\widehat{𝝈}𝑯).`$
Here, the Hamiltonian $`\widehat{H}^v`$ should be considered as the $`2\times 2`$ matrix acting on the spinor vector $`𝚿^v`$ rather than the $`6\times 6`$ matrix Hamiltonian acting on the six component wave function as in Ref. lut, . Correspondingly, $`\widehat{𝑰}=\{\widehat{I}_x,\widehat{I}_y,\widehat{I}_z\}`$ in Eq. (15) is the vector operator. It is straightforward to show that in this representation $`(\widehat{𝑰}𝑻)𝚿^v=i[𝑻\times 𝚿^v]`$, where $`𝑻`$ is an arbitrary vector. The terms proportional to $`\mathrm{\Delta }`$ in Hamiltonian (15) describe the effect of the spin–orbit coupling and $`\kappa =\kappa ^LE_p/6E_g`$,pb  where $`\kappa ^L`$ is the magnetic Luttinger parameter.lut  One can find that $`\kappa =2/3`$ from the relation:pb ; dkk  $`\kappa ^L=(2\gamma _1^L+2\gamma _2^L+3\gamma _3^L)/3`$, where the effective mass Luttinger parameters,lut  $`\gamma _{1,2,3}^L`$, can be presented as: $`\gamma _1^LE_p/3E_g`$ and $`\gamma _2^L\gamma _3^LE_p/6E_g`$ in the approximation used above.pb

### II.2 Linear Zeeman effect as a perturbation

Following the perturbation approach developed in Ref. kiselev, , we present the Hamiltonian (12) as:

$$\widehat{H}_{PB}(\widehat{𝒌})=\widehat{H}^0(\widehat{𝒑})+\widehat{H}^{^{}}(\widehat{𝒑},𝑯),$$
(16)
where the Hamiltonian $`\widehat{H}^0`$ describes the electron states in zero magnetic field:

$`\widehat{H}^0(\widehat{𝒑})=\left(\begin{array}{cc}\frac{\alpha }{2m_0}\widehat{U}_2\widehat{p}^2& iP\widehat{U}_2\widehat{𝒑}\\ iP\widehat{U}_2\widehat{𝒑}& \frac{1}{3}\mathrm{\Delta }(\widehat{𝑰}\widehat{𝝈})\left(E_g+\frac{1}{3}\mathrm{\Delta }\right)\widehat{U}_2\end{array}\right),`$ (19)
and the Hamiltonians $`\widehat{H}^{^{}}`$ describes the effect of a weak external magnetic field. Linear in the magnetic field terms of $`\widehat{H}^{^{}}(\widehat{𝒑},𝑯)`$ can be written:

$$\widehat{H}^{^{}}(\widehat{𝒑},H)=\mu _BH\widehat{G}+\frac{e}{c}\{𝑨,\widehat{𝑽}\}\mu _BH(\widehat{G}+\widehat{G}^{^{}}),$$
(20)
where $`\{a,b\}=1/2(ab+ba)`$ denotes an anticommutator and $`\widehat{𝑽}=\widehat{H}^0(𝒑)/𝒑`$ is the envelope velocity operator. The operators $`\widehat{G}`$ and $`\widehat{G}^{^{}}`$ are defined as:

$`\widehat{G}=\left(\begin{array}{cc}\frac{1}{2}g^{}(\widehat{𝝈}𝒏)& 0\\ 0& (\widehat{𝑰}𝒏)\widehat{U}_2+\frac{1}{2}g_0(\widehat{𝝈}𝒏)\end{array}\right),`$ (23)
$`\widehat{G}^{^{}}=\left(\begin{array}{cc}\alpha (\widehat{𝑳}𝒏)& iP{\displaystyle \frac{m_0}{\mathrm{}}}[𝒏\times 𝒓]\\ iP{\displaystyle \frac{m_0}{\mathrm{}}}[𝒏\times 𝒓]& 0\end{array}\right)\widehat{U}_2,`$ (26)
where $`𝒏=𝑯/H`$ is the unit vector directed along the external magnetic field, and $`\widehat{𝑳}=\frac{1}{\mathrm{}}\left[𝒓\times \widehat{𝒑}\right]`$ is the envelope angular momentum operator.

Generally, the calculation of the linear Zeeman effect for the carriers confined in a $`3D`$ external potential of arbitrary shape is a straightforward theoretical problem. The same procedure is used for an impurity potential and for a zero dimensional quantum dot of an arbitrary shape. Using the unperturbed Hamiltonian $`\widehat{H}^0`$ one has to find first the energy levels $`E_\lambda `$ and the corresponding eigen functions $`\mathrm{\Psi }_\lambda =\{\mathrm{\Psi }^c,𝚿^v\}`$ of the carrier in the external confining potential. Then, the effect of the magnetic field can be found perturbatively:

$$\mathrm{\Delta }E_\lambda =\mu _BH\left[\mathrm{\Psi }_\lambda |\widehat{G}|\mathrm{\Psi }_\lambda +\mathrm{\Psi }_\lambda |\widehat{G}^{^{}}|\mathrm{\Psi }_\lambda \right].$$
(27)
where the wave functions should be normalized $`\mathrm{\Psi }_\lambda |\mathrm{\Psi }_\lambda =1`$. Substituting $`\mathrm{\Psi }_\lambda `$ into this expression we obtain:

$$\mathrm{\Delta }E_\lambda =\mathrm{\Delta }E_c+\mathrm{\Delta }E_v+\mathrm{\Delta }E_{coup},$$
(28)
where the contribution of the valence and conduction bands to Zeeman effect $`\mathrm{\Delta }E_c`$ and $`\mathrm{\Delta }E_v`$ correspondingly are:

$`{\displaystyle \frac{\mathrm{\Delta }E_c}{\mu _BH}}={\displaystyle \frac{1}{2}}\mathrm{\Psi }^c|g^{}(\widehat{𝝈}𝒏)|\mathrm{\Psi }^c+\mathrm{\Psi }_\mu ^c|\alpha (\widehat{𝑳}𝒏)|\mathrm{\Psi }_\mu ^c,`$ (29)
$`{\displaystyle \frac{\mathrm{\Delta }E_v}{\mu _BH}}={\displaystyle \frac{1}{2}}𝚿^v|g_0(\widehat{𝝈}𝒏)|𝚿^v+𝚿_\mu ^v|(\widehat{𝑰}𝒏)|𝚿_\mu ^v,`$ (30)
and the coupling correction is given by

$`{\displaystyle \frac{\mathrm{\Delta }E_{coup}}{\mu _BH}}`$ $`=`$ $`\mathrm{\Psi }^c|i{\displaystyle \frac{m_0P}{\mathrm{}}}\widehat{U}_2[𝒏\times 𝒓]|𝚿^v`$ (31)
$`+`$ $`\mathrm{\Psi }^c|i{\displaystyle \frac{m_0P}{\mathrm{}}}\widehat{U}_2[𝒏\times 𝒓]|𝚿^v^{}.`$
In principle, this straightforward approach allows us to find the linear Zeeman splitting of the energy levels in any arbitrarily shaped hetero-nanostructure. However, the calculations of the zero field wave functions $`\mathrm{\Psi }_\lambda `$ for arbitrary shape heterostructure is a rather cumbersome procedure and, consequently, the Zeeman splitting calculation that uses these wave functions is very complicated. In the present paper, from hereafter, only spherical semiconductor nanocrystals are considered. The high symmetry of these quantum dots allow us to calculate the Zeeman splitting of the QSLs.

## III Energy levels of the electron confined in bare spherical nanocrystals

### III.1 General boundary conditions for the envelope wave functions

We will consider bare semiconductor nanocrystals which surface can be modeled by an impenetrable barrier. To find unperturbed envelope wave functions that are described by the Hamiltonians of Eq. (19) in the bulk region one should impose an appropriate boundary conditions on these functions at the nanocrystal surface. For the impenetrable barrier the general boundary conditions (GBCs) have been shown in Ref. bc,  to guarantee the vanishing of the normal to the surface component of the envelope flux density matrix. In a spherical nanocrystal the normal envelope flux density matrix, $`J_\tau ^{\lambda \eta }(𝒓)`$, should vanish at any point of the nanocrystals surface:

$`J_\tau ^{\lambda \eta }(𝒓)|_{r=a}𝝉𝑱^{\lambda \beta }|_{r=a}=`$
$`{\displaystyle \frac{1}{2}}\left[(\mathrm{\Psi }_\lambda ,𝝉\widehat{𝑽}\mathrm{\Psi }_\eta )+(𝝉\widehat{𝑽}\mathrm{\Psi }_\lambda ,\mathrm{\Psi }_\eta )\right]|_{r=a}=0,`$ (32)
where $`a`$ is the nanocrystal radius and $`𝝉=𝒓/r`$ (in spherical coordinates $`𝒓`$ is defined as $`𝒓(r,\mathrm{\Theta },\phi )`$). This general requirement of Eq. (32) should be satisfied for two arbitrarily chosen eigenfunctions $`\mathrm{\Psi }_\lambda `$ and $`\mathrm{\Psi }_\eta `$ of the Hamiltonian $`\widehat{H}^0`$ defined in Eq. (19) with energies $`E_\lambda `$ and $`E_\eta `$, respectively. Substituting the explicit expressions for the normal components of the envelope velocities $`𝝉\widehat{𝑽}=𝝉\widehat{H}^0/𝒑`$ into Eq. (32) one obtains:

$`J_\tau ^{\lambda \eta }(𝒓)|{}_{r=a}{}^{}={\displaystyle \frac{i\mathrm{}}{2m_0}}[\alpha (\mathrm{\Psi }_\eta ^c𝝉\mathbf{}\mathrm{\Psi }_\lambda ^c\mathrm{\Psi }_\lambda ^c𝝉\mathbf{}\mathrm{\Psi }_\eta ^c)`$
$`+{\displaystyle \frac{2m_0P}{\mathrm{}}}(𝝉𝚿_\eta ^v\mathrm{\Psi }_\lambda ^c𝝉𝚿_\lambda ^v\mathrm{\Psi }_\eta ^c)\left]\right|_{r=a}=0.`$ (33)
Using equation $`\widehat{H}^0\mathrm{\Psi }=E\mathrm{\Psi }`$ one can express the components of the spin vector $`𝚿^v`$ through $`\mathbf{}\mathrm{\Psi }^c`$:

$`𝚿^v`$ $`=`$ $`{\displaystyle \frac{\mathrm{}}{2m_0P}}\left(\alpha {\displaystyle \frac{m_0}{m_c(E)}}\right)\mathbf{}\mathrm{\Psi }^c`$ (34)
$`+`$ $`{\displaystyle \frac{i\mathrm{}}{4m_0P}}\left(g_c(E)g^{}\right)[\widehat{𝝈}\times \mathbf{}\text{ }\mathrm{\Psi }^c],`$
where the energy dependent electron effective mass $`m_c(E)`$ and $`g`$–factor $`g_c(E)`$ are defined in Eqs. (14) and (3) respectively. The normal projection $`(𝝉𝚿^v)`$ can then be written:

$`𝝉𝚿^v(𝐫)`$ $`=`$ $`{\displaystyle \frac{\mathrm{}}{2m_0P}}\left(\alpha {\displaystyle \frac{m_0}{m_c(E)}}\right){\displaystyle \frac{\mathrm{\Psi }^c}{r}}`$ (35)
$``$ $`{\displaystyle \frac{\mathrm{}}{4m_0Pr}}\mathrm{\Delta }g(E)(\widehat{𝝈}\widehat{𝑳})\mathrm{\Psi }^c,`$
where $`\mathrm{\Delta }g(E)=g^{}g_c(E)`$. Substituting Eq. (35) into Eq. (33) one obtains the general requirement for the conduction band component of the envelope wave function at the NC surface:

$`J_\tau ^{\lambda \eta }(a)={\displaystyle \frac{i\mathrm{}}{2m_0}}[({\displaystyle \frac{m_0}{m(E_\lambda )}}\mathrm{\Psi }_\eta ^c{\displaystyle \frac{\mathrm{\Psi }_\lambda ^c}{r}}{\displaystyle \frac{m_0}{m(E_\eta )}}\mathrm{\Psi }_\lambda ^c{\displaystyle \frac{\mathrm{\Psi }_\eta ^c}{r}})+`$
$`{\displaystyle \frac{1}{2r}}(\mathrm{\Psi }_\eta ^c\mathrm{\Delta }g(E_\lambda )(\widehat{𝝈}\widehat{𝑳})\mathrm{\Psi }_\lambda ^c\mathrm{\Psi }_\lambda ^c\mathrm{\Delta }g(E_\eta )(\widehat{𝝈}\widehat{𝑳})\mathrm{\Psi }_\eta ^c)\left]\right|_{r=a}=0.`$ (36)
Equation (36) must be fulfilled at each point of the surface. It is satisfied for all arbitrary chosen energy states $`\lambda `$ and $`\eta `$ if and only if the boundary conditions for $`\mathrm{\Psi }_\lambda ^c`$ as well as for $`\mathrm{\Psi }_\eta ^c`$ are given by:

$`\mathrm{\Psi }^c(r=a,\mathrm{\Theta },\phi )=Ta_0({\displaystyle \frac{m_0}{m_c(E)}}{\displaystyle \frac{\mathrm{\Psi }^c(r,\mathrm{\Theta },\phi )}{r}}+`$
$`{\displaystyle \frac{1}{2r}}\mathrm{\Delta }g(E)(\widehat{𝝈}\widehat{𝑳})\mathrm{\Psi }^c(r,\mathrm{\Theta },\phi )\left)\right|_{r=a},`$ (37)
where $`T`$ is a real number constant independent of $`E`$ and $`a_0`$ is the lattice constant. We assume that the surface of the nanocrystal also possesses the spherical symmetry and is characterized by the same BCs at any point of the surface. In this case parameter $`T`$ in the GBCs of Eq. (37) is independent of angles $`\mathrm{\Theta }`$ and $`\phi `$.

### III.2 Electron energy levels: the surface induced spin–orbit splitting

Let us consider the effect of the GBCs of Eq. (37) on the electron QSLs in the absence of a magnetic field. Using Eq. (34) that expresses the valence band component $`𝚿^v`$ of the wave function through its conduction band component $`\mathrm{\Psi }^c`$ one can derive the bulk Schrödinger equation describing $`\mathrm{\Psi }^c`$ inside a semiconductor nanocrystal:

$$\frac{\mathrm{}^2}{2m_c(E)}\widehat{U}_2\mathbf{}^2\mathrm{\Psi }^c(𝒓)=E\mathrm{\Psi }^c(𝒓).$$
(38)
One can see that each spin component of $`\mathrm{\Psi }^c`$ is a solution of the standard bulk Schrödinger equation with the energy dependent effective mass $`m_c(E)`$. Equation (38) does not contain a spin-orbit term and its solution can always be presented as $`f_l(r)Y_{l,l_z}(\mathrm{\Theta },\phi )`$, where $`l`$ and $`l_z`$ are the angular momentum and angular momentum projection, correspondingly, $`Y_{l,l_z}(\mathrm{\Theta },\phi )`$ are the spherical harmonics, and the radial function $`f_l(r)`$ satisfies to the following equation:

$`{\displaystyle \frac{\mathrm{}^2}{2m_c(E)}}\mathrm{\Delta }_lf_l(r)=Ef_l(r),`$ (39)
$`\mathrm{\Delta }_l={\displaystyle \frac{^2}{^2r}}+{\displaystyle \frac{2}{r}}{\displaystyle \frac{}{r}}{\displaystyle \frac{l(l+1)}{r^2}}.`$
At the same time the GBCs of Eq. (37) mixes two electron spin sublevels, and all electron states are characterized now by the total angular momentum: $`𝒋=𝑳+𝑺`$. As a result $`\mathrm{\Psi }^c`$ is an eigen spinor of the operator of the total angular momentum:

$`\mathrm{\Psi }^c=f_l^\pm (r)\mathrm{\Omega }_{j,l,m}(\mathrm{\Theta },\phi ),`$ (40)
where $`\mathrm{\Omega }_{j,l,m}(\mathrm{\Theta },\phi )`$ are the spherical spinors, $`j`$ and $`m`$ are the total angular momentum and its projection respectively, and $`l`$ is the angular momentum of the electron state. The two radial functions $`f_l^\pm `$ describe the two electron states with $`j=l\pm 1/2`$ (note that the states described by $`f_l^{}`$ exist only for $`l1`$). We use the definition of the spherical spinors as in Ref. ll,

$`\mathrm{\Omega }_{j,l,m}=\left(\begin{array}{c}C_{1/2,1/2;l,m1/2}^{j,m}Y_{l,m1/2}\\ C_{1/2,1/2;l,m+1/2}^{j,m}Y_{l,m+1/2}\end{array}\right),`$ (43)
where $`j=l\pm 1/2`$ and $`C_{j1,m1;j2,m2}^{j,m}`$ are the Clebsch-Gordan coefficients. Substituting Eq. (40) into Eq. (37) one can write the general boundary condition for the radial wave functions $`f_l^\pm (r)`$:

$`f_l^\pm (a)=Ta_0\left[{\displaystyle \frac{m_0}{m_c(E)}}f_l^\pm ^{}(a)+\delta k_l^\pm f_l^\pm (a)\right],`$ (44)
where

$`\delta k_l^+={\displaystyle \frac{l}{2a}}\mathrm{\Delta }g(E),l=0,1,2\mathrm{},`$ (45)
for the states with $`j=l+1/2`$ and

$`\delta k_l^{}={\displaystyle \frac{l+1}{2a}}\mathrm{\Delta }g(E),l=1,2,3\mathrm{},`$ (46)
for the states with $`j=l1/2`$. The conventionally used standard BCs for the impenetrable barrier assumes vanishing of the wave function $`\mathrm{\Psi }^c`$ at the nanocrystal surface, and thus correspond to $`Ta_0=0`$. In general, however, the conduction band component of the wave function does not vanish at the surface. Furthermore, it has been shown in Ref.bc,  that the boundary condition with $`Ta_0=0`$ is incorrect in cases where interband coupling is important. The appropriate value of $`Ta_0`$ should be determined from the fitting to the experimental data.

The solutions of Eq. (39) can be written as $`f_l^\pm (r)=(C_l^\pm /a^{3/2})j_l(\varphi _{l,n}^\pm r/a)`$, where $`j_l`$ are spherical Bessel functions, $`C_l^\pm `$ is the normalization constant determined by the condition $`(|\mathrm{\Psi }^c|^2+|𝚿^v|^2)𝑑V=1`$, and $`\varphi _{l,n}^\pm `$ is connected with the energy, $`E`$, of the electron level: $`E=\mathrm{}^2\varphi _{l,n}^{\pm 2}/2m_c(E)a^2`$. An equation that determined $`\varphi _{l,n}^\pm `$ is obtained by substitution of $`f_l^\pm (r)`$ into the BCs of Eq. (44):

$`j_l(\varphi _{l,n}^\pm )\left[1\delta k_l^\pm Ta_0\right]=`$ (47)
$`{\displaystyle \frac{Ta_0}{a}}{\displaystyle \frac{m_0}{m_c(E)}}\varphi _{l,n}^\pm `$ $`\left[{\displaystyle \frac{l}{2l+1}}j_{l1}(\varphi _{l,n}){\displaystyle \frac{l+1}{2l+1}}j_{l+1}(\varphi _{l,n})\right].`$
The $`n^{\mathrm{th}}`$ solution of this equation defines the energy of the $`n^{\mathrm{th}}`$ electron level with the angular momentum $`l`$ and the total angular momentum $`j=l\pm 1/2`$. In the case of the standard BCs $`Ta_0=0`$, and the solution $`\varphi _{l,n}^\pm `$ is the $`n`$–th zero $`\varphi _{l,n}^0`$ of the spherical Bessel functions $`j_l`$. The general BCs with $`Ta_00`$ takes into account the effect of the surface on the electron energy levels that is important in small nanocrystals. In large nanocrystals satisfying the condition $`a|Ta_0|(m_0/m_c)`$, the solutions $`\varphi _{l,n}^\pm `$ are close to $`\varphi _{l,n}^0`$ and the effect of the surface on the confined electron states is negligible.

The electron states with $`j=l+1/2`$ and $`j=l1/2`$ have different energies for $`l1`$ as a result of the general BCs of Eq. (44). This difference describes the surface induced spin–orbit splitting of the excited states: $`\mathrm{\Delta }_c=E_{l+1/2}E_{l1/2}`$. It can be shown that $`\mathrm{\Delta }_c`$ is positive if the spin–orbit splitting of the valence band $`\mathrm{\Delta }>0`$.

Figure 1 shows the effect of the general BCs on the energy of the ground $`1S`$ ($`l=0`$) and the first excited $`1P`$ ($`l=1`$) electron states in bare CdSe nanocrystals. The surface induced spin-orbit interaction splits the last state into two states with the total angular momentum $`j=3/2`$ ($`P_{3/2}`$ state) and $`j=1/2`$ ($`P_{1/2}`$ state) and the size dependence of this splitting $`\mathrm{\Delta }_c=E(1P_{3/2})E(1P_{1/2})`$ is shown in Fig. 1(b). The calculations have been performed for the following bulk parameters of CdSe: $`E_p=19.0`$ eV and $`m_c(0)=0.116`$ $`m_0`$ from Ref. seisyan, , $`E_g=1.839`$ eV, $`\mathrm{\Delta }=0.42`$ meV, and $`g_c(0)=0.68`$ from Ref. Landoldt, , that result in $`\alpha =1.07`$ and $`g^{}=1.96`$. One can see that even a small surface parameter introduced by the GBCs, $`|Ta_0|=0.6`$ $`\AA `$, significantly affects both ground and excited states in small nanocrystals. The positive (negative) value of the surface parameter $`Ta_0>0`$ ($`Ta_0<0`$) increases (decreases) the energy of all states in comparison with $`Ta_0=0`$. The relative order of the $`P_{3/2}`$ and $`P_{1/2}`$ states with the total momentum $`j=3/2`$ and $`j=1/2`$ always coincides with the relative order of the valence band subbands characterized by the same total momentum. The value of the spin-orbit splitting, $`\mathrm{\Delta }_c`$, however, remains for all excited states much smaller than the averaged energy $`E_l=(lE_{l1/2}+(l+1)E_{l+1/2})/(2l+1)`$ of the level with the orbital momentum $`l`$.

If $`|\delta k_l^\pm Ta_0|1`$, the averaged energies $`E_l`$ and corresponding wave numbers $`\varphi _{l,n}`$ can be found from the simplified BCs given by Eqs. (44, 47) with $`\delta k_l^\pm =0`$. The energy corrections $`\mathrm{\Delta }E_l^\pm `$ coming from the small $`\delta k_l^\pm 0`$ can be found perturbatively. In the Appendix we obtain the following energy corrections:

$`\mathrm{\Delta }E_l^\pm ={\displaystyle \frac{\mathrm{}^2}{2m_0}}|f_l^\pm (a)|^2a^2\delta k_l^\pm =`$
$`{\displaystyle \frac{\mathrm{}^2}{4m_0}}{\displaystyle \left(\mathrm{\Delta }g(E)\mathrm{\Psi }^c(\widehat{𝝈}\widehat{𝑳})\mathrm{\Psi }^c\right)\frac{1}{r}𝑑S},`$ (48)
where $`dS=r^2sin(\mathrm{\Theta })d\mathrm{\Theta }d\phi `$. Note that although $`\varphi _{l,n}^+=\varphi _{l,n}^{}=\varphi _{l,n}`$, the normalization constants $`C_l^+C_l^{}`$ . However, in the considered approximation they can be replaced with high accuracy by the averaged constant $`C_l=C_l^+=C_l^{}`$ that is determined by the approximate normalization condition:

$`{\displaystyle _0^a}|f_l|^2r^2𝑑r+{\displaystyle _0^a}|\mathrm{\Phi }_l|^2r^2𝑑r=1,`$ (49)
$`|\mathrm{\Phi }_l|^2`$ $`=`$ $`{\displaystyle \frac{\mathrm{}^2}{2m_0E_p}}\left(\alpha {\displaystyle \frac{m_0}{m_c(E)}}\right)^2\left(|f_l^{^{}}|^2+{\displaystyle \frac{l(l+1)}{r^2}}|f_l|^2\right),`$
that neglects the second term in Eq. (34). Thus, if $`|\delta k_l^\pm Ta_0|1`$, $`\mathrm{\Delta }_c<E_l`$, the energy levels of the excited states $`E_l^\pm `$ with $`j=l\pm 1/2`$ are the eigen energies of the effective Hamiltonian $`\widehat{H}_l`$:

$`\widehat{H}_l\mathrm{\Omega }_{l\pm 1/2,l,m}=E_l^\pm \mathrm{\Omega }_{l\pm 1/2,l,m},`$
$`\widehat{H}_l=E_l\widehat{U}_2+{\displaystyle \frac{1}{2l+1}}\mathrm{\Delta }_c(E_l)\left(\widehat{𝑳}\widehat{𝝈}\right)`$ (50)
where the energy dependent spin–orbit splitting $`\mathrm{\Delta }_c(E_l)`$ is given by

$`\mathrm{\Delta }_c(E_l)=\left(l+{\displaystyle \frac{1}{2}}\right){\displaystyle \frac{\mathrm{}^2}{2m_0a^2}}\mathrm{\Sigma }_{sur}(E_l),`$ (51)
$`\mathrm{\Sigma }_{sur}(E_l)=\mathrm{\Delta }g(E_l)a^3|f_l(a)|^2=\mathrm{\Delta }g(E_l)C_l^2j_l^2(\varphi _{l,n}).`$ (52)
The approximate expressions of Eqs. (51,52) describe the exact splitting $`\mathrm{\Delta }_c(E_1)`$ of the $`1P`$ states in CdSe nanocrystals shown in Fig. 1(b) with high accuracy (the largest error in the smallest nanocrystals is about $`2\%`$ for $`Ta_0=0.6`$ $`\AA `$). It is important to note here that while the matrix elements of the spin–orbit operator $`(\widehat{𝑳}\widehat{𝝈})`$ are nonzero only for $`l1`$, Eq. (52) defines also the surface parameter $`\mathrm{\Sigma }_{sur}`$ for the $`l=0`$ $`S`$ symmetry states.

The dimensionless parameter $`\mathrm{\Sigma }_{sur}`$ is proportional to the spin–orbit splitting in the valence band $`\mathrm{\Delta }`$ and to the square of the wave function at the surface. It describes the surface–induced spin–orbit coupling of the conduction electron QSLs in bare semiconductor nanocrystals. In bulk semiconductors the integration in Eq. (48) results in zero spin–orbit splitting of the conduction band states because it must be carried out at the remote bounding surface where the wave function is vanishing. $`\mathrm{\Sigma }_{sur}=0`$ if one assumes the vanishing of the conduction band component wave function at the surface of spherical nanocrystals. This assumption is never justified if the coupling between conduction band and valence band components is significant. Thus, the spin–orbit splitting of the electron QSLs is caused by the admixture of the valence band states near the surface.

## IV The fine structure of electron QSLs in a magnetic field

### IV.1 Surface induced magnetic moment of the confined electrons

Let us consider now the energy of the electron QSLs, $`E_l^\pm `$, in a weak magnetic field. Substituting the zero field wave functions $`\mathrm{\Psi }=\{\mathrm{\Psi }^c,𝚿^v\}`$ given by Eq. (40) and (34) into Eqs. (29) and (31), we obtain for the energy correction $`\mathrm{\Delta }E\mathrm{\Delta }E_c+\mathrm{\Delta }E_{coup}`$:

$`\mathrm{\Delta }E=\mu _BH[{\displaystyle \frac{1}{2}}\mathrm{\Psi }^c|g_c(E)(\widehat{𝝈}𝒏)|\mathrm{\Psi }^c+`$
$`\mathrm{\Psi }^c|{\displaystyle \frac{m_0}{m_c(E)}}(\widehat{𝑳}𝒏)|\mathrm{\Psi }^c]+\mathrm{\Delta }E_{sur},`$ (53)
where we neglect $`\mathrm{\Delta }E_v`$ corrections of Eq. (30) as being smaller by the factor $`E_l/(E_l+E_g)`$. The second term of Eq. (53) describes the unexpected surface contribution to the electron magnetic energy:

$`\mathrm{\Delta }E_{sur}={\displaystyle \frac{\mu _BH}{4}}{\displaystyle 𝑑S\frac{1}{r}\mathrm{\Delta }g(E_l)(\mathrm{\Psi }^c[𝒓\times [\widehat{𝝈}\times 𝒓]]\mathrm{\Psi }^c)}.`$ (54)
The effective Hamiltonian describing the fine structure of the electron state with the orbital momentum $`l`$ in a magnetic field can be written as $`\widehat{H}_l+\widehat{H}_H`$, where $`\widehat{H}_l`$ is defined by Eq. (50) and the effect of a weak magnetic field is described by:

$`\widehat{H}_H={\displaystyle \frac{1}{2}}\mu _B\overline{g}_s(E_l)(\widehat{𝝈}𝑯)+\mu _B\overline{g}_l(E_l)(\widehat{𝑳}𝑯)+`$
$`{\displaystyle \frac{1}{4}}\mu _B\mathrm{\Sigma }_{sur}(E_l)([𝝉\times [\widehat{𝝈}\times 𝝉]𝑯).`$ (55)
Here the weighted spin $`\overline{g}_s`$ and orbital $`\overline{g}_l`$ $`g`$ factors are given by

$`\overline{g}_s`$ $`=`$ $`{\displaystyle _0^a}g_c(E_l)r^2𝑑r|f_l(r)|^2,`$ (56)
$`\overline{g}_l`$ $`=`$ $`{\displaystyle _0^a}m_0/m_c(E_l)r^2𝑑r|f_l(r)|^2,`$ (57)
respectively. The first two terms in Eq. (55) describe the averaged volume energy of the spin $`𝝁_S=\mu _B\overline{g}_s(E_l)𝑺`$ and orbital $`𝝁_L=\mu _B\overline{g}_l(E_l)\widehat{𝑳}`$ magnetic moments in an external magnetic field, and the last term describes the energy of the surface–induced magnetic moment $`𝝁_{sur}(E_l)`$ given by:

$`𝝁_{sur}={\displaystyle \frac{\mu _B}{4}}\mathrm{\Sigma }_{sur}(E_l)[𝝉\times [\widehat{𝝈}\times 𝝉].`$ (58)
This magnetic moment arises from the surface–induced spin–orbital term of Eq. (50) which is modified by the Larmor precession of the electron in an external magnetic field. Indeed, the surface energy term $`\mathrm{\Delta }E_{sur}=(𝝁_{sur}𝑯)`$ can be obtained directly by replacing $`i\mathbf{}\text{ }i\mathbf{}+(e/c\mathrm{})𝑨`$ in the spin–orbit perturbation term $`(\widehat{𝑳}\widehat{𝝈})=i([𝒓\times \mathbf{}]\widehat{𝝈})`$ of Eq. (50). The origin of the surface–induced electron magnetic moment is similar to those of an additional relativistic magnetic moment of the electron in atoms, and their values are derived in a similar way (see for example Refs. bethe, ; abragam, ; margenau, ). It is necessary to note that the surface-induced magnetic moment $`𝝁_{sur}`$ does not vanish for the states with $`l=0`$ even when it arises from the spin–orbit coupling term $`(\widehat{𝑳}\widehat{𝝈})`$.

### IV.2 Size dependence of the ground state electron $`g`$ factor

All electron states that have $`S`$ symmetry are Kramers doublets that are degenerate with respect to its spin projection. The external magnetic field lifts this degeneracy and splits these states into two levels with energy:

$$E_0(H)=E_0\pm \frac{1}{2}\mu _Bg_s(E_0)H,$$
(59)
where the $`\pm `$ signs correspond to the electron states with spins parallel and antiparallel to the magnetic field direction. The spin effective $`g`$ factor can be obtained from Eq. (55) as:

$`g_s(E_0)=\overline{g}_s(E_0)+{\displaystyle \frac{1}{3}}\mathrm{\Sigma }_{sur}.`$ (60)
The effective electron $`g`$ factor for the $`S`$ electron states in spherical heterostructures, $`g_s(E_0)`$, was first obtained in Ref. kiselev,  where the standard BCs at the heterointerface were used to describe the size dependence of the electron $`g`$ factor. In the case of the bare semiconductor nanocrystals the standard BC at the surface ($`f_0(a)=0`$) would lead to zero surface contribution to the effective electron $`g`$ factor. We have examined here the effect of the general BC of Eq. (44) on the electron effective $`g`$ factor in CdSe nanocrystals. The weighted $`g`$ factor of the states with $`S`$ symmetry in Eq. (60) can be written:

$$\overline{g}_s(E)=g_0+_0^ar^2𝑑r|f_l(r)|^2\left(g_c(E)g_0\right),$$
(61)
where the corrections $`\mathrm{\Delta }E_v`$ of Eq. (30) to the $`\overline{g}_s`$ of Eq. (56) have been added. Figure 2 shows the size dependence of the ground state electron $`g`$ factor, $`g_s(E_0)`$, calculated using the standard BC with $`|Ta_0|=0`$ and the general BC with $`|Ta_0|=0.6`$ $`\AA `$. One can see that the experimental size dependence of the electron $`g`$-factor taken from Ref. gupta02,  is described very well by the general BC with the negative parameter $`Ta_0=0.6`$, while the use of the positive parameter brings the theoretical curve far away from the data.

The size dependence of the bulk–like energy–dependent $`g`$ factor, $`g_c(E_0)`$, calculated with the help of Eq. (3) for $`Ta_0=0`$ is also shown in Fig. 2. One can see that the bulk $`g`$–factor $`g_c`$ fails to describe the experimental data even in the largest dots. At the same time, the difference between two $`g_s`$ curves calculated with $`Ta_0=0.6`$ $`\AA `$ and $`Ta_0=0`$ is not very large. This is because the general BCs affects the electron g-factor in two ways: indirectly, through the change of the zero field energy $`E_0`$ decreasing/increasing the electron g-factor, and directly, through the surface contribution $`1/3\mathrm{\Sigma }_{sur}(1S)`$, that is always positive. In the case of the negative $`Ta_0<0`$ the GBCs decreases the energy of the ground electron state decreasing the electron g-factor, and these two effects partly compensate for each other. However, the surface contribution $`1/3\mathrm{\Sigma }_{sur}(1S)`$ calculated with $`Ta_0=0.6`$ $`\AA `$ is significant in small nanocrystals (see Fig. 3).

### IV.3 Symmetry of the confined electron excited states in an external magnetic field

The fine structure of the excited electron states in an external magnetic field is very sensitive to the relation between $`\mathrm{\Delta }_c(E_l)`$ and the energy of the orbital magnetic moment $`\overline{g}_l\mu _BH`$. In the low–field regime, when the magnetic energy is smaller than the separation between the electron states with $`j=l\pm 1/2`$, the external magnetic field satisfying the condition $`\overline{g}_l\mu _BH\mathrm{\Delta }_c`$ splits the levels according to projection $`m`$ of the full momentum $`j`$ on the magnetic field as:

$`E_{j,m}^+=E_l+\mathrm{\Delta }_c(E_l){\displaystyle \frac{l}{2l+1}}+\mu _Bg_j^+(E_l)mH,`$ (62)
for $`j=l+1/2`$ and

$`E_{j,m}^{}=E_l\mathrm{\Delta }_c(E_l){\displaystyle \frac{l+1}{2l+1}}+\mu _Bg_j^{}(E_l)mH.`$ (63)
for $`j=l1/2`$. The effective electron $`g`$–factors

$`g_j^+`$ $`=`$ $`{\displaystyle \frac{1}{2j}}\overline{g}_s(E_l)+{\displaystyle \frac{2j1}{2j}}\overline{g}_l(E_l)+{\displaystyle \frac{2j+1}{8j(j+1)}}\mathrm{\Sigma }_{sur},`$ (64)
$`g_j^{}`$ $`=`$ $`{\displaystyle \frac{1}{2(j+1)}}\overline{g}_s(E_l)+{\displaystyle \frac{2j+3}{2(j+1)}}\overline{g}_l(E_l){\displaystyle \frac{2j+1}{8j(j+1)}}\mathrm{\Sigma }_{sur}`$
are the analogs of the Lande factors for electrons in atoms in the case of the ”anomalous” Zeeman effect.bethe  The surface contributions to the electron $`g`$–factors ($`\mathrm{\Sigma }_{sur}`$) are similar to the relativistic corrections in Refs. abragam, ; margenau, .

When the zero field fine structure splitting becomes smaller than the energy of the orbital magnetic moment, the magnetic field Zeeman term mixes the states with different $`j=l\pm 1/2`$. In this case the projections of the spin momentum $`s_z`$ and orbital momentum $`l_z`$ on the direction of the magnetic field are a more convenient notation for describing the electron state fine structure. The spin–orbit term $`(𝑳𝑺)`$ and the additional surface moment $`(𝝁_{sur}𝑯)`$ may, however, mix the states with different values of the $`s_zl_z`$ product.

Let us consider the matrix elements of the surface magnetic moment operator $`𝝁_{sur}`$ on the eigen-functions of one angular momentum $`l`$. Assuming that the states with different $`l`$ are not mixed, one can find:

$`{\displaystyle \frac{r_ir_j}{r^2}}Y_{l,m}(\mathrm{\Theta },\phi )=({\displaystyle \frac{2l1+2l^2}{(2l+3)(2l1)}}\delta _{ij}`$
$`{\displaystyle \frac{2}{(2l+3)(2l1)}}\{L_iL_j\})Y_{l,m}(\mathrm{\Theta },\phi ),`$ (66)
where $`i,j=x,y,z`$ and $`\delta _{ij}`$ is the Kronecker delta symbol. Substituting Eq. (66) into $`(𝑯[𝝉\times [\widehat{𝝈}\times 𝝉])=(𝑯\widehat{𝝈})(𝑯𝝉)(𝝉\widehat{𝝈})`$, we rewrite the magnetic field Hamiltonian $`\widehat{H}_H`$ of Eq. (55) as:

$`\widehat{H}_H=\mu _Bg_s(E_l)(𝑺𝑯)+\mu _B\overline{g}_l(E_l)(𝑳𝑯)+`$
$`\mu _B\mathrm{\Sigma }_{sur}(E_l){\displaystyle \frac{(𝑺𝑯)\widehat{L}^2+\{(𝑺𝑳)(𝑳𝑯)\}}{(2l+3)(2l1)}}.`$ (67)
Here the spin electron $`g`$ factor is given by

$$g_s(E_l)=\overline{g}_s(E_l)\frac{1}{(2l+3)(2l1)}\mathrm{\Sigma }_{sur}(E_l).$$
(68)
The matrix elements of the last term in Eq. (67) are zero for $`l=0`$. If $`\mathrm{\Sigma }_{sur}(E_l)\overline{g}_l(E_l)`$ one can neglect the off diagonal elements of the operator $`\{(𝑺𝑳)(𝑳𝑯)\}`$ and replace them with $`(𝑺𝑯)(𝑳𝒏)^2`$. This is the case for the first excited $`1P`$ state in CdSe nanocrystals (for comparison, see the corresponding curves in Figs. 3 and 4). In this case the last term of Eq. (67) describes the surface contribution to the spin splitting of the electron levels that depends on the projection of the orbital momentum on the magnetic field.errow

In the strong field regime (similar to the case of the ”quasi–normal” Zeeman effect or ”complete” Paschen-Back effect for the electrons in atomsbethe ) one can additionally neglect the off diagonal elements of the spin–orbit operator $`(𝑳𝑺)`$. The fine structure of the electron level with orbital momentum $`l`$ is described by:

$`E_{l,l_z,s_z}=E_l+{\displaystyle \frac{2s_zl_z}{2l+1}}\mathrm{\Delta }_c(E_l)+`$ (69)
$`\mu _Bs_zg_s(E_l,l_z)H+\mu _Bl_z\overline{g}_l(E_l)H,`$
where $`l_z=l,\mathrm{}0,\mathrm{}l`$ and $`s_z=\pm 1/2`$ are the projection of the electron angular momentum and spin on the magnetic field direction and

$$g_s(E_l,l_z)=\overline{g}_s(E_l)+\frac{l^2+l+l_z^21}{(2l+3)(2l1)}\mathrm{\Sigma }_{sur}(E_l).$$
(70)
Thus the structures of the excited QSLs with $`l1`$ may be different in weak and strong magnetic fields and undertake the anticrossing in the intermediate magnetic field (similar to those known for atomsbethe ). In nanocrystals the weak, intermediate and strong field regimes depend strongly on the nanocrystal size as well as on its surface conditions.

## V Discussion and Conclusion

We have studied the effect of general boundary conditions (the surface effect) on the electron QSLs and their Zeeman splitting in spherical bare semiconductor nanocrystals. The above consideration that has been carried on in the eight–band effective mass model can be easily extended to describe spherically layered heterostructures and wide gap semiconductor nanocrystals, which are better described by the fourteen–band model (see for example Ref. emrspaper, ).

Comparing the results of our theoretical calculation with the experimental size dependence of the electron $`g`$-factor we have determined the surface parameter $`Ta_0=0.6\pm 0.05`$ $`\AA `$ in bare CdSe nanocrystals. Fitting the experimental data, we used $`E_p=19.0`$ eV, that has been obtained independently from bulk measurementsseisyan  and that describes better the experimental data than $`E_p=17.5`$ eV, previously used for CdSe in Refs. josa, ; norris, . The surface parameter $`Ta_0`$ characterizes the electronic properties of the surface and should be considered as the additional one to the set of parameters that describes the bulk properties of semiconductors. In CdSe nanocrystals prepared by a different technique $`Ta_0`$ can be different.

The extracted absolute value and the negative sign of $`Ta_0=0.6`$ $`\AA `$ is consistent with our theoretical expectations for $`Ta_0`$ in studied CdSe nanocrystals. Its value is very close to the theoretical value of the surface parameter for semiconductors with a symmetrical band structurebc  $`|(Ta_0)_s|a^{}=\sqrt{\mathrm{}^2/2E_pm_0}0.45`$ $`\AA `$. It can also be shown within the eight band effective mass model, that the negative sign of the surface parameter does not allow the existence of the surface localized states with $`E<0`$ (gap states) (one can find similar consideration in Ref. bc, ). Indeed, the CdSe samples studied in Refs. gupta, ; gupta02,  show very high PL quantum efficiency and do not show deep gap transitions. The negative parameter $`Ta_0`$ leads also to an additional nonparabolicity, bowing the size dependence of the electron energy levels (see Fig. 1) and therefore may describe the unexplained experimental size dependence of the 1S electron level in small CdSe nanocrystals.norris

Using the GBCs we have found also the direct surface contribution to the spin–orbit effects in zero and weak external magnetic fields. The surface contribution to the zero field spin–orbit splitting is similar to the interface contribution obtained in Refs. bassani, ; vasko,  for $`2D`$ electrons in planar quantum wells by using the spin–dependent boundary conditions. It has been pointed out in Ref. bassani,  that the interface contribution to the Rashba spin–orbit term in the $`2D`$ Hamiltonianrashba  is related to discontinuity of the band parameters at the semiconductor heterointerface and that this contribution is an additional one to those connected with the space charge and/or the external electric field. The importance of the effects described by the Rashba term for the 2D electrons confined near the curved surfaceentin ; romanov  and cylindrical semiconductor quantum dotsvosk  has been emphasized recently. The Rashba spin–orbit term in our spherical dots is a direct consequence of the GBCs for the envelope function. The same consideration can be made for cylindrical dots or any other nanostructure geometry (the results will be published elsewhere). The GBCs provide an important connection between the constant that describes the magnitude of the spin–orbit term and surface conditions in nanostructures.

In conclusion, we have shown an important influence of the semiconductor surface on the electron energy structure in bare spherical nanocrystals. The effect of the surface has been modeled through the choice of the boundary condition parameter that describes the nonzero value of the envelope function at the nanocrystal surface. The additional nonparabolicity of the quantum size energy levels, the spin–orbit splitting of the electron quantum size levels, and the additional magnetic moment of the electrons have been shown to be induced by the surface. The effects are significant in small nanocrystals and their considerations require a multiband effective mass approach because interband coupling is important there. The analysis of the experimental data allows us to determine the appropriate parameter of the boundary conditions that characterize the surface in studied bare CdSe semiconductor nanocrystals.

###### Acknowledgements.

The authors thank I. A. Merkulov and B. K. Meyer for helpful discussions and J. Tischler for a critical reading of the manuscript. The work of A. V. Rodina was supported in part by the Alexander von Humboldt Foundation, Deutsche Forschungsgemeinschaft (DFG) and the Swiss National Science Foundation. Al. L. Efros thanks the U.S. Office of Naval Research (ONR), U.S. Department of Energy (DOE), and the DARPA/QuIST program for financial support. A. Yu. Alekseev acknowledges support from the Swiss National Science Foundation and of the grant of INTAS 99-1705.

*

## Appendix A Effect of the small surface perturbation on the quantum size level energy in spherical nanocrystals

We are interested in deriving a variation of the electron level energy $`E`$ caused by a small variation of the parameter $`\varsigma `$ that characterizes the surface BC for the bulk wave function $`f(r,\varsigma )`$. The GBCs at the spherical surface of the nanocrystal with radius $`r=a`$ can be written as

$$f^{^{}}(a,\varsigma )=f(a,\varsigma )A(\varsigma ),$$
(71)
where $`A(\varsigma )`$ is the real number constant. The function $`f(r,\varsigma )`$ is the solution of bulk Schrödinger equation $`D\widehat{k}^2f(r,\varsigma )=E(\varsigma )f(r,\varsigma )`$ where the constant $`D`$ is independent of $`\varsigma `$. Taking a derivative of the Schrödinger equation on $`\varsigma `$, multiplying both parts of the resulting equation by $`f^{}`$ and integrating it over the sphere volume, one can obtain:

$$\frac{E}{\varsigma }=Da^2\left(\frac{f}{\varsigma }f^{{}_{}{}^{}}\frac{f^{^{}}}{\varsigma }f^{}\right)|_{r=a}.$$
(72)
Taking a derivative of Eq. (71) and substituting $`f^{^{}}(a,\varsigma )/\varsigma =A(\varsigma )/\varsigma f(a,\varsigma )+A(\varsigma )f(a,\varsigma )/\varsigma `$ into Eq. (72) one arrives at the final expression for the energy variation:

$$\frac{E}{\varsigma }=D\frac{A(\varsigma )}{\varsigma }|f(a)|^2a^2.$$
(73)
Substituting $`D=\mathrm{}^2/2m_c(E_l)`$ and $`A(\varsigma )=m_c(E_l)/m_0\left[1/(Ta_0)+\varsigma \right]`$ with $`\varsigma =\delta k_l^\pm (E_l)`$ into this equation we obtain Eq. (48) for the energy correction $`\mathrm{\Delta }E_l^\pm `$ to the averaged energy of the electron level with the orbital momentum $`l`$ caused by the small perturbation of the boundary conditions of Eq. (44).