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# Filtrations on Chow Groups and Transcendence Degree

For a smooth complex projective variety $`X`$ defined over a number field, we have filtrations on the Chow groups depending on the choice of realizations. If the realization consists of mixed Hodge structure without any additional structure, we can show that the obtained filtration coincides with the filtration of Green and Griffiths, assuming the Hodge conjecture. In the case the realizations contain Hodge structure and etale cohomology, we prove that if the second graded piece of the filtration does not vanish, it contains a nonzero element which is represented by a cycle defined over a field of transcendence degree one. This may be viewed as a refinement of results of Nori, Schoen, and Green-Griffiths-Paranjape. For higher graded pieces we have a similar assertion assuming a conjecture of Beilinson and Grothendieck’s generalized Hodge conjecture.

Chow group, Deligne cohomology, cycle map

Introduction

Let $`X_{}`$ be a smooth complex projective variety, and $`\text{CH}^p(X_{})_{}`$ be the Chow group with rational coefficients. Choosing a category $``$ of realizations (see , , ), we can define a filtration $`F_{}`$ on $`\text{CH}^p(X_{})_{}`$ by spreading cycles out, see (1.4) below (and also $`[1],[16],[25],[29])`$. By definition $`F_{}^1\text{CH}^p(X_{})_{}`$ consists of null homologous cycles, and $`F_{}^2\text{CH}^p(X_{})_{}`$ is contained in the kernel of the Abel-Jacobi map (tensored with $``$). It is conjectured that the filtration $`F_{}`$ does not depend on the choice of $``$, and coincides with Murre’s conjectural filtration . We can verify this conjecture, assuming a conjecture of Beilinson on the injectivity of the Abel-Jacobi map for smooth projective varieties over number fields  together with the Hodge conjecture.

In this paper we assume that $`X_{}`$ is defined over a number field $`k`$. Then a similar filtration has been defined by M. Green and P. Griffiths , and we have

0.1. Proposition. If $``$ is the category of mixed Hodge structure without any additional structure, then the filtration $`F_{}`$ coincides with the filtration $`F_G`$ of Green and Griffiths , assuming the Hodge conjecture.

Let $`X`$ be a smooth projective $`k`$-variety whose base change by $`k`$ is $`X_{}`$. Let $`K`$ be a subfield of $``$ containing $`k`$, and having finite transcendence degree. Let $`X_K`$ be the base change of $`X`$ by $`kK`$. Then $`\text{CH}^p(X_K)_{}`$ is identified with a subgroup of $`\text{CH}^p(X_{})_{}`$, and has the induced filtration $`F_{}`$. It has been observed by Green and Griffiths  that the property of this induced filtration is very much influenced by the transcendence degree $`d`$ of $`K`$. For example, $`\text{Gr}_F_{}^r\text{CH}^p(X_K)_{}`$ vanishes for $`r>d+1`$ if the realization consists of mixed Hodge structure. If $`d=0`$, it is conjectured that $`F_{}^2\text{CH}^p(X_K)_{}=0`$ by the above conjecture of Beilinson. However, for $`d=1`$, it is shown by M. Nori and C. Schoen  that the kernel of the Albanese map for certain surfaces has a nontrivial cycle defined over a subfield $`K`$ of transcendence degree $`1`$. Here we can show also the nonvanishing of $`\text{Gr}_F_{}^2\text{CH}^2(X_{})_{}`$ (see ), which implies that the above estimate is optimal. The results of Nori and Schoen are recently generalized by Green-Griffiths-Paranjape  to the case of surfaces having a nontrivial global $`2`$-form. Considering these, we may have

0.2. Conjecture. If $`\text{Gr}_F_{}^r\text{CH}^p(X_{})_{}0`$ with $`r1`$, then it contains a nonzero element which is represented by a cycle defined over a subfield of transcendence degree $`r1`$.

In this paper we prove

0.3. Theorem. Assume that the realizations contain mixed Hodge structure and étale cohomology with Galois action. Then Conjecture (0.2) is true for $`r=1,2`$. Assume further that Grothendieck’s generalized Hodge conjecture holds, and the filtration $`F_{}`$ coincides with the filtration $`F_{\text{MHS}}`$ associated to the category of realization consisting of mixed Hodge structure. Then Conjecture (0.2) is true also for $`r3`$.

The proof uses Terasoma’s argument on Hilbert’s irreducibility theorem  as in . The same argument was also indicated by A. Tamagawa when we tried to construct an $`l`$-adic theory of normal functions . It is quite interesting that we cannot prove Theorem (0.3) by using only Hodge theory. The hypothesis of (0.3) for $`r=2`$ is satisfied for $`0`$-cycles if $`X`$ has a nontrivial global $`2`$-from  (this follows from Murre’s Albanese motive  and Bloch’s diagonal cycle ). So Theorem (0.3) may be viewed as a refinement of the result of Green-Griffiths-Paranjape . For cycles of arbitrary codimension, we have a similar assertion if the standard conjecture of Lefschetz-type holds for $`X`$.

If we restrict to the subgroup $`\text{CH}_{\text{alg}}^p(X_{})_{}`$ consisting of cycles algebraically equivalent to zero, $`F_{}^2`$ coincides with the kernel of the Abel-Jacobi map (or that of the $`l`$-adic Abel-Jacobi map). This applies to the case of $`0`$-cycles on surfaces, and we have in general $`\text{Gr}_F_{}^r\text{CH}^p(X_{})_{}=0`$ for $`r>p`$ (see also ). However it is not yet clear whether the nonvanishing of the kernel of the Albanese map for a surface $`X_{}`$ implies that $`\text{Gr}_F_{}^2\text{CH}^2(X_{})_{}0`$, because it is not proved that the filtration $`F_{}`$ is separated.

I would like to thank L. Barbieri-Viale, A. Rosenschon and A. Tamagawa for useful discussions.

1. Filtrations on Chow groups

1.1. Realizations. We will denote by $``$ a category of (systems of) realizations, see , , , etc. The simplest example in our case is the abelian category MHS of $``$-mixed Hodge structures whose graded pieces $`\text{Gr}_m^W`$ are polarizable . In this paper we choose a number field $`k`$ contained in $``$. Then we have the category $`\text{MHS}_k`$ of mixed $``$-Hodge structures with $`k`$-structure, see , , etc. Let $`\overline{k}`$ be the algebraic closure of $`k`$ in $``$, and put $`G=\text{Gal}(\overline{k}/k)`$. For a prime number $`l`$, we have an abelian category $`_l`$ whose object consists of filtered vector spaces $`(H_{},W)`$ over $``$, $`(H_l,W)`$ over $`_l`$ and $`(H_{},F)`$ over $``$ together with isomorphisms

$$\alpha _l:(H_{},W)_{}_l=(H_l,W),\alpha _{}:H_{}_{}=H_{},$$

where $`(H_l,W)`$ is endowed with a continuous action of $`G`$ and $`(\text{Gr}_m^WH_{},\text{Gr}_m^W(H_{},F))`$ is a polarizable $``$-Hodge structure of weight $`m`$ for any $`m`$ (here $`W`$ denotes also the induced filtration on $`H_{})`$, see , , , etc. We assume that polarizations are compatible with the Galois action to assure the semisimplicity of pure objects.

For other examples, we have $`_{\text{ét}}`$ by considering $`H_l`$ for any prime numbers $`l`$, and $`_{k,l},_{k,\text{ét}}`$ by considering also the $`k`$-structure. It is also possible to consider the category of systems of realizations as in .

Note that the category $``$ can be extended naturally to the category of mixed sheaves $`(S/k)`$ for any $`k`$-variety $`S`$, and there is a forgetful functor from $`(S/k)`$ to the category of perverse sheaves , see  for the details.

1.2. Deligne cohomology. Let $``$ be one of the categories of realizations as in (1.1). Let $`X`$ be a smooth $`k`$-variety. Then the cohomology $`H^i(X/k,)`$ is well-defined in $``$, using de Rham cohomology of $`X_k`$, étale cohomology of $`X_{\overline{k}}`$, and cohomology of $`X_{}`$ together with comparison isomorphisms, see , , , etc. Furthermore, there exists canonically $`K_{}(X/k)`$ in the bounded derived category $`D^b`$ whose cohomology is isomorphic to the cohomology of $`X`$ (using, for example, two sets of affine open coverings associated to general hyperplane sections , see also \[25, 1.1\]).

We define Deligne cohomology by

$$H_𝒟^i(X/k,(j))=\text{Hom}_{D^b}(,K_{}(X/k)(j)[i]),$$

where $`(j)`$ is the Tate twist, and $`[i]`$ is the shift of complexes. If $`=\text{MHS}`$, it is called the absolute $`p`$-Hodge cohomology in . If $`=\text{MHS}`$ or $`\text{MHS}_k`$, then higher extension groups vanish in $``$ as a corollary of  (see ), and we have canonical short exact sequences

$`0\text{Ext}_{}^1(,H^{i1}(X/k,)(j))`$ $`H_𝒟^i(X/k,(j))`$ $`(\mathrm{1.2.1})`$
$`\text{Hom}_{}(,H^i(X/k,)(j))0.`$
For a closed subvariety $`Z`$ of $`X`$, we can define similarly the Deligne local cohomology $`H_{𝒟,Z}^i(X/k,(j))`$ using a complex $`K_{,Z}(X/k)`$, which is the shifted mapping cone of $`K_{}(X/k)K_{}((XZ)/k)`$.

We have the cycle map

$$cl:\text{CH}^p(X)_{}H_𝒟^{2p}(X/k,(p)),$$
$`(\mathrm{1.2.2})`$
which is compatible with the usual cycle class map to $`H^{2p}(X_{},)(p)`$. Its restriction to the null homologous cycles coincides with Griffiths’ Abel-Jacobi map  tensored with $``$ if $`k=`$, $`=\text{MHS}`$ and $`X`$ is smooth proper, see , , , , etc. We can show that (1.2.2) is compatible with the direct image by a proper morphism and the pull-back by any morphism, and hence with the action of a correspondence, cf. .

1.3. Leray filtration. Let $`X,S`$ be a smooth $`k`$-varieties. Then the Deligne cohomology $`H_𝒟^i(X\times _kS/k,(j))`$ has the (decreasing) Leray filtration $`F_L`$ induced by the canonical filtration $`\tau `$ on $`K_{}(X/k)`$ using the canonical isomorphism

$$K_{}(X\times _kS/k)=K_{}(X/k)K_{}(S/k).$$

Here $`F_L^r`$ on $`H_𝒟^i(X\times _kS/k,(j))`$ is induced by $`\tau _{ir}`$ as in . Assume $`X`$ is smooth proper. Then the filtration $`F_L`$ splits because we have a non canonical isomorphism

$$K_{}(X/k)\underset{j}{}H^j(X/k,)[j]\text{in}D^b.$$
$`(\mathrm{1.3.1})`$
(This follows from a general property of pure complexes, see e.g. .) In particular, for a morphism $`S^{}S`$, the filtration $`F_L`$ is strictly compatible with the pull-back morphism

$$H_𝒟^i(X\times _kS/k,(j))H_𝒟^i(X\times _kS^{}/k,(j)).$$

By the canonical filtration on $`K_{}(S/k)`$, we have for each $`m`$ the Leray spectral sequence

$`E_2^{p,q}`$ $`=\text{Ext}_{}^{pm}(,H^m(X/k,)H^q(S/k,)(j))`$ $`(\mathrm{1.3.2})`$
$`\text{Gr}_{F_L}^{p+qm}H_𝒟^{p+q}(X\times _kS/k,(j))`$
It is conjectured that this degenerates at $`E_2`$, because $`K_{}(S/k)`$ would be defined in the (conjectural) category of motives where higher extension groups should vanish so that a decomposition similar to (1.3.1) would hold.

We will denote by $`F_L^{}`$ the decreasing filtration on $`\text{Gr}_{F_L}^rH_𝒟^i(X\times _kS/k,(j))`$ induced by the canonical filtration $`\tau `$ on $`K_{}(S/k)`$ so that $`\text{Gr}_{F_L^{}}^s\text{Gr}_{F_L}^rH_𝒟^i(X\times _kS/k,(j))`$ is a subquotient of $`\text{Ext}_{}^s(,H^{ir}(X/k,)H^{rs}(S/k,)(j))`$.

In the case $`=\text{MHS}`$ or $`\text{MHS}_k`$, the higher extension groups really vanish so that (1.3.2) degenerates at $`E_2`$ and we get canonical short exact sequences

$`0\text{Ext}_{}^1(,H^{ir}(X/k,)H^{r1}(S/k,)(j))\text{Gr}_{F_L}^rH_𝒟^i(X\times _kS/k,(j))`$ $`(\mathrm{1.3.3})`$
$`\text{Hom}_{}(,H^{ir}(X/k,)H^r(S/k,)(j))0.`$
In particular, $`F_L^2\text{Gr}_{F_L}^r=0`$ in this case.

1.4. Filtration on Chow groups. Let $`X`$ a smooth $`k`$-variety, and $`K`$ be a subfield of $``$ containing $`k`$, and having finite transcendence degree over $`k`$. Put $`X_K=X_kK`$, and $`X_{}=X_k`$. Then we have natural injections

$$\text{CH}^p(X_K)_{}\text{CH}^p(X_{})_{},$$
$`(\mathrm{1.4.1})`$
and $`_K\text{CH}^p(X_K)_{}=\text{CH}^p(X_{})_{}`$.

Let $`\zeta \text{CH}^p(X_K)_{}`$. By spreading out , there exists an irreducible smooth affine $`k`$-variety $`S`$ such that $`k(S)=K`$ and $`\zeta `$ is defined over $`S`$, i.e. there exists $`\zeta _S\text{CH}^p(X\times _kS)_{}`$ whose restriction to $`X_K`$ is $`\zeta `$, where $`X_K`$ is identified with the generic fiber of $`X\times _kS`$ $`S`$. For an open subvariety $`S^{}`$ of $`S`$, let $`\zeta _S^{}`$ denote the restriction of $`\zeta _S`$ over $`S^{}`$. Then the limit of $`\zeta _S^{}`$ is well-defined, see .

Let $`k_S`$ be the algebraic closure of $`k`$ in $`\mathrm{\Gamma }(S,𝒪_S)`$, and put $`S_{}=S_{k_S}`$. This is an irreducible variety, i.e. $`S`$ is geometrically irreducible over $`k_S`$. (If we consider $`S_k`$ instead of $`S_{k_S}`$, then the former is a disjoint union of copies of the latter in the case $`k_S`$ is a normal extension of $`k`$.) Note that $`X\times _kS=X_{k_S}\times _{k_S}S`$, and this allows us to replace $`k`$ with $`k_S`$. Actually we can replace $`k`$ with any finite extension, because we take the limit over $`K`$.

The cycle map (1.2.2) induces

$$cl:\text{CH}^p(X\times _kS)_{}H_𝒟^{2p}(X\times _kS/k_S,(p)),$$
$`(\mathrm{1.4.2})`$
and the filtration $`F_{}`$ on $`\text{CH}^p(X\times _kS)_{}`$ is defined to be the induced filtration by the Leray filtration $`F_L`$ on $`H_𝒟^{2p}(X\times _kS/k_S,(p))`$. Then, taking the inductive limit over the non empty open subvarieties of $`S`$, we get the filtration $`F_{}`$ on $`\text{CH}^p(X_K)_{}`$.

This means that $`\zeta F_{}^r\text{CH}^p(X_K)_{}`$ if $`cl(\zeta _S)F_L^rH_𝒟^{2p}(X\times _kS/k_S,(p))`$ for some $`S`$, and hence $`\text{Gr}_F_{}^r\zeta `$ is nonzero in $`\text{Gr}_F_{}^r\text{CH}^p(X_K)_{}`$ if the restrictions of $`\text{Gr}_{F_L}^rcl(\zeta _S)`$ to $`\text{Gr}_{F_L}^rH_𝒟^{2p}(X\times _kS^{}/k_S,(p))`$ does not vanish for any non empty open subvarieties $`S^{}`$ of $`S`$.

We can show that $`F_{}`$ is strictly compatible with the base change by $`KK^{}`$, see . This implies that $`\text{CH}^p(X)_{}`$ has the filtration $`F_{}`$ which is strictly compatible with (1.4.1).

1.5. Filtration of Green and Griffiths. In the case $`=\text{MHS}`$, a similar filtration is constructed by M. Green and P. Griffiths . They assume that the $`S`$ in (1.4) are smooth projective, and then, roughly speaking, consider everything modulo ambiguity coming from cycles over proper closed subvarieties of $`S`$ (here they also assume Grothendieck’s generalized Hodge conjecture). More precisely, for a smooth projective $`k`$-variety $`S`$ and a divisor $`Z`$ of $`S`$ defined over $`k_S`$, we have an exact sequence

$$\text{CH}^{p1}(X\times _kZ)_{}\text{CH}^p(X\times _kS)_{}\text{CH}^p(X\times _k(SZ))_{}0,$$
$`(\mathrm{1.5.1})`$
and the filtration $`F_G`$ of Green and Griffiths on $`\text{CH}^p(X\times _k(SZ))_{}`$ is defined to be the quotient filtration of $`F_{}`$ on $`\text{CH}^p(X\times _kS)_{}`$, where $`=\text{MHS}`$. Then we take the inductive limit as before.

1.6. Proposition. $`F_G=F_{}`$, assuming the Hodge conjecture.

Proof. It is enough to show the assertion on $`\text{CH}^p(X\times _k(SZ))_{}`$. This is reduced to the case $`Z`$ is a divisor with normal crossings by using an embedded resolution. We have a canonical morphism of (1.5.1) to

$$H_{𝒟,Z}^{2p}(X\times _kS/k_S,(p))H_𝒟^{2p}(X\times _kS/k_S,(p))H_𝒟^{2p}(X\times _k(SZ)/k_S,(p)).$$

Here we may assume $`k_S=k`$ (and similarly for intersections of irreducible components of $`Z`$) replacing $`k`$ if necessary. Assuming the Hodge conjecture, we have to prove the following:

For $`\zeta F_{}^r\text{CH}^p(X\times _kS)_{}`$ such that $`\text{Gr}_{F_L}^rcl(\zeta )\text{Gr}_{F_L}^rH_𝒟^{2p}(X\times _kS,(p))`$ comes from $`\xi \text{Gr}_{F_L}^rH_{𝒟,Z}^{2p}(X\times _kS,(p))`$, there exists $`\zeta ^{}\text{CH}^{p1}(X\times _kZ)_{}`$ such that the image of $`cl(\zeta ^{})`$ in $`H_𝒟^{2p}(X\times _kS,(p))`$ belongs to $`F_L^r`$, and coincides with $`\text{Gr}_{F_L}^rcl(\zeta )`$ modulo $`F_L^{r+1}`$.

This is verified by using correspondences $`\mathrm{\Gamma }_a\text{CH}^{dimS1}(S\times _k\stackrel{~}{Z})_{}`$ such that

$$(\mathrm{\Gamma }_a)_{}:H^j(S,)H^{j2}(\stackrel{~}{Z},)(1)$$

vanishes for $`ja`$, and the restriction of $`i_{}(\mathrm{\Gamma }_a)_{}`$ to $`\text{Im}i_{}H^a(S,)`$ is the identity for $`j=a`$, where $`\stackrel{~}{Z}`$ is the normalization of $`Z`$. Indeed, if we denote by

$$\xi _0\text{Hom}_{\text{MHS}}(,H^{2pr}(X,)H_Z^r(S,)(p))$$

the image of $`\xi `$ by the canonical morphism, then the Hodge conjecture implies the existence of $`\zeta ^{}\text{CH}^{p1}(X\times _k\stackrel{~}{Z})_{}`$ such that the Künneth component of the cycle class of $`\zeta ^{}`$ in $`\text{Hom}(,H^{2pa}(X,)H_Z^a(S,)(p))`$ coincides with $`\xi _0`$ for $`a=r`$, and is zero otherwise. We may assume further that the image of $`cl(\zeta ^{})`$ in $`H_𝒟^{2p}(X\times _kS,(p))`$ belongs to $`F_L^r`$ by modifying $`\zeta ^{}`$ using $`\mathrm{\Gamma }_a`$ for $`a<r`$ together with the decomposition (1.3.1). So the assertion is reduced to the case $`\xi _0=0`$ by modifying $`\zeta `$ using $`\zeta ^{}`$. Then the assertion follows by using $`\mathrm{\Gamma }_a`$ for $`a=r`$.

2. Proof of Theorem (0.3)

2.1. Hilbert’s irreducibility theorem. We first recall Terasoma’s argument  on Hilbert’s irreducibility theorem, which is essential for the proof of (0.3). Let $`U`$ be a non empty open subvariety of $`_k^1`$, and

$$0L\stackrel{~}{L}_{l,U}0$$
$`(\mathrm{2.1.1})`$
be a short exact sequence of smooth $`_l`$-sheaves on $`U`$, where $`_{l,U}`$ denotes the constant sheaf of rank one on $`U`$. Put $`K=k(U)`$, and let $`\overline{K}`$ be an algebraic closure of $`K`$. There exists a $`k`$-valued point $`x`$ of $`U`$ such that (2.1.1) splits if and only if its restriction over $`x`$ does. Indeed, choosing a geometric point over $`x`$ on each Galois étale covering of $`U`$ in a compatible way with natural projections, we get a morphism of $`\text{Gal}(\overline{k}/k)`$ to $`\pi _1(U,\text{Spec}\overline{K})`$, and hence to the arithmetic monodromy group of $`\stackrel{~}{L}`$. Then we have infinitely many $`k`$-valued points $`x`$ such that the last morphism is surjective by Hilbert’s irreducibility theorem  together with the structure of the $`l`$-adic monodromy group , see . Related to the $`l`$-adic theory of normal functions, the same argument was indicated by A. Tamagawa, see .

Here it is also possible to get infinitely many $`k`$-valued points $`x`$ such that the above property holds for the monodromy groups of $`L`$ and $`\stackrel{~}{L}`$ simultaneously by the theory of Hilbert set. Note also that the exact sequence (2.1.1) can be replaced by a short exact sequence $`0L^1\stackrel{~}{L}L^00`$ of smooth $`_l`$-sheaves, because

$$\text{Ext}^1(L^0,L^1)=\text{Ext}^1(_{l,U},om(L^0,L^1)).$$

2.2. Restriction of extension classes. Let $`f:SU`$ be a smooth projective morphism of smooth irreducible $`k`$-varieties where $`U`$ is a non empty open subvariety of $`_k^1`$. Let $`n=dimS1`$, and $`L=R^nf_{}_X(U/k)`$ where $`(U/k)`$ denotes the category of mixed sheaves on $`U`$ (shifted by $`dimU)`$, and $`L`$ is pure of weight $`n`$, see . Here we assume that there is a forgetful functor from $``$ to $`_l`$ in (1.1). By semisimplicity we have a direct sum decomposition

$$L=L^{}L^{\prime \prime }\text{in}(U/k)$$

such that $`H^0(U/k,L^{})=0`$ and $`L^{\prime \prime }`$ is constant over $`\text{Spec}k`$ (i.e. the pull-back of an object on $`\text{Spec}k`$ by the structure morphism).

Let $`H`$ be a pure object of weight $`n+1`$ in $``$ (e.g. a direct factor of $`H^i(X/k,)(q)`$ for a smooth projective $`k`$-variety $`X`$ where $`i2q=n+1`$). Let $`H_U=a_U^{}H`$, where $`a_U:U\text{Spec}k`$ is the structure morphism. By the adjunction for $`a_U`$, we have a natural isomorphism

$$\text{Ext}_{(U/k)}^1(H_U,L)=\text{Hom}_{D^b}(H,(a_U)_{}L[1]).$$

This implies

$`\text{Ext}_{(U/k)}^1(H_U,L^{})`$ $`=\text{Hom}_{}(H,H^1(U/k,L^{})),`$ $`(\mathrm{2.2.1})`$
$`\text{Ext}_{(U/k)}^1(H_U,L^{\prime \prime })`$ $`=\text{Ext}_{}^1(H,L_x^{\prime \prime }),`$
for any $`k`$-valued point $`x`$ of $`U`$, because $`\text{Hom}_{}(H,H^1(U/k,L^{\prime \prime }))=0`$.

Let $`\xi \text{Hom}_{}(H,H^1(U/k,L^{}))`$. The corresponding extension class is denoted also by $`\xi `$. If $`\xi 0`$, there exists a $`k`$-valued point $`x`$ of $`U`$ such that the restriction $`\xi _x`$ of $`\xi `$ to $`x`$ does not vanish by (2.1), because (2.2.1) holds also for $`l`$-adic sheaves. Note that the same argument still holds after replacing $`k`$ by a finite extension. In the case $`dimS=1`$ and $`n=0`$, we may also assume that $`f^1(x)`$ consists of one point. Then replacing $`U,L`$ with $`S,_{l,S}`$, the restriction of $`\xi `$ to some $`k`$-valued point of $`S`$ does not vanish (replacing $`k`$ if necessary).

2.2. Restriction to open subvarieties. With the above notation and assumptions, let $`S_x=f^1(x)`$. Then $`L_x^{}`$ is a direct factor of $`H^n(S_x/k,)`$, and we get

$$\xi _x\text{Ext}_{}^1(H,H^n(S_x/k,)).$$

We now consider to restrict $`\xi _x`$ to a non empty open subvariety $`S_x^{}`$ of $`S_x`$. We assume that the underlying Hodge structure of $`H`$ does not have a nontrivial subobject with level $`<n`$, where the level of a Hodge structure is the difference between the maximal and minimal numbers $`p`$ such that $`\text{Gr}_F^p0`$ (and the difference between level and weight is even). Let

$$H^{}=H^n(S_x^{}/k,).$$

It has weights $`n`$. If $`S_x^{}`$ is sufficiently small,we have

$$W_nH^{}=H^n(S_x/k,)/N^1H^n(S_x/k,),$$

where $`N`$ is the ‘coniveau’ filtration. By semisimplicity there exists a subobject $`H^{\prime \prime }`$ such that

$$H^n(S_x/k,)=N^1H^n(S_x/k,)H^{\prime \prime }.$$

We have $`\text{Hom}_{}(H,H^{}/W_nH^{})=\text{Hom}_{}(H,\text{Gr}_{n+1}^WH^{})=0`$, because $`\text{Gr}_{n+1}^WH^{}`$ has level $`<n`$ (see ). Then, using the long exact sequence associated to

$$0W_nH^{}H^{}H^{}/W_nH^{}0,$$
$`(\mathrm{2.3.1})`$
we see that the restriction of $`\xi _x`$ to $`S_x^{}`$ does not vanish if $`\xi _x`$ does not come from $`\text{Ext}_{}^1(H,N^1H^n(S_x/k,))`$ (i.e. if its image in $`\text{Ext}_{}^1(H,H^{\prime \prime })`$ does not vanish).

In the case $`dimS=2`$ and $`n=1`$, the last condition is trivially satisfied because $`N^1H^1(S_x/k,)=0`$. Furthermore, $`H^{}/W_nH^{}`$ is a direct sum of copies of $``$, replacing $`k`$ with a finite extension (depending on $`S_x^{})`$ if necessary. Indeed, it is given by taking a basis of the kernel of the cycle class map $`_i[D_i]H^2(S_x/k,)(1)`$ where the $`D_i`$ are the irreducible components of $`S_xS_x^{}`$, which may be assumed to be absolutely irreducible (replacing $`k`$ if necessary). This fact will be used in (2.4).

In general, $`L_{1,x}^{}:=N^1H^n(S_x/k,)L_x^{}`$ does not vanish. However, it corresponds to a $`_l`$-submodule stable by the action of $`\text{Gal}(\overline{k}/k)`$, and is hence extended to an étale subsheaf $`L_1^{}`$ of $`L^{}`$ by the argument in (2.1). Let $`s=\text{rank}L_1^{}`$. Then taking the pull-back to $`U_{}`$, it determines a subsheaf with $``$-coefficients, and the latter underlies a variation of Hodge structure. Indeed, $`^sL_1^{}`$ determines a variation of Hodge structure of rank $`1`$ contained in $`^sL^{}`$ by the global invariant cycle theorem (using a finite covering if necessary, because the monodromy of $`^sL_1^{}`$ is defined over $``$ and is finite, see ). Then $`L_1^{}`$ is the kernel of $`L^{}^{s+1}L^{}`$ defined locally by a generator of $`^sL_1^{}`$, and hence underlies a variation of Hodge structure.

This argument implies that the restriction of $`\xi _x`$ to $`S_x^{}`$ does not vanish if $`\xi \text{Hom}_{}(H,H^1(U/k,L^{}))`$ is nonzero. Indeed, if the restriction vanishes, the corresponding $`l`$-adic extension class comes from $`L_{1,x}^{}(L_x^{})`$ which is extended to $`L_1^{}(L^{})`$. We apply some argument in (2.1) also to $`L^{}/L_1^{}`$, where we may assume $`H=`$ by the last remark of (2.1) and the monodromy group of the extension for $`L^{}/L_1^{}`$ is a quotient of that for $`L^{}`$. Then we see that $`\xi `$ comes from $`\text{Hom}(H,H^1(U/k,L_1^{}))`$, where Hom is considered in $`_l`$. But $`H^1(U/k,L_1^{})`$ has level $`<n`$, because the stalk of $`L_1^{}`$ has level $`n2`$, see . So $`\xi `$ vanishes by the hypothesis on the level of $`H`$, and the assertion follows.

2.4. Proof of (0.3). By hypothesis there exists a smooth irreducible affine $`k`$-variety $`S`$ together with $`\zeta \text{CH}^p(X\times _kS)_{}`$ such that its cycle class $`cl(\zeta )`$ in $`H_𝒟^{2p}(X\times _kS/k,(p))`$ belongs to $`F_L^r`$, and the restriction of $`\text{Gr}_{F_L}^rcl(\zeta )`$ to $`\text{Gr}_{F_L}^rH_𝒟^{2p}(X\times _kS^{}/k,(p))`$ does not vanish for any non empty open subvariety $`S^{}`$ of $`S`$. Using the spectral sequence (1.3.2), $`\text{Gr}_{F_L}^rcl(\zeta )`$ induces

$$\xi _0\text{Hom}_{}(,H^{2pr}(X/k,)H^r(S^{}/k,)(p)).$$

We first consider the case where $`\xi _0`$ does not vanish for any $`S^{}`$. Let $`d=dimXp`$. Since $`\xi _0`$ corresponds to the morphism

$$\xi _0^{}:H^{2d+r}(X/k,)(d)H^r(S^{}/k,)),$$

this nonvanishing is equivalent to that the image of $`\xi _0^{}`$ has level $`r`$ (assuming Grothendieck’s generalized Hodge conjecture for $`r>2`$). So we may assume $`dimS=r`$ by the weak Lefschetz theorem. Put $`n=r1`$. Let

$$H=H^{2d+r}(X/k,)(d),$$

and $`H_{<n}`$ be the largest subobject of $`H`$ which has level $`<n`$. By semisimplicity there exists a subobject $`H_{>n}`$ with a decomposition $`H=H_{<n}H_{>n}`$, and the restriction of $`\xi _0^{}`$ to $`H_{>n}`$ does not vanish. So the assertion follows from (2.2-3) applied to a Lefschetz pencil.

Now we may assume $`\xi _0=0`$, i.e. $`\text{Gr}_{F_L}^rcl(\zeta )F_L^1\text{Gr}_{F_L}^r`$, see (1.3). Then $`\text{Gr}_{F_L}^rcl(\zeta )`$ induces

$`\xi _1`$ $`\text{Ext}_{}^1(,H^{2pr}(X/k,)H^{r1}(S^{}/k,)(p))`$
$`=\text{Ext}_{}^1(H,H^{r1}(S^{}/k,)).`$
Consider the case where $`\xi _1`$ does not vanish for any $`S^{}`$. If $`r=1`$, we may replace $`S^{}`$ with any point (replacing $`k`$ if necessary), and the assertion is clear. So we may assume $`r>1`$. In this case we have to show the nonvanishing of its restriction to any non empty open subvariety $`C^{}`$ of a general hyperplane section $`\overline{C}`$ of a smooth projective compactification $`\overline{S}`$ of $`S`$.

If $`r=2`$, let $`𝒫_{\overline{S}/k},𝒫_{\overline{C}/k}`$ be the Picard variety of $`\overline{S},\overline{C}`$. Then we have an injective morphism of $`k`$-varieties $`𝒫_{\overline{S}/k}𝒫_{\overline{C}/k}`$, and any $`k`$-valued point on the image can be lifted to a $`k`$-valued point of $`𝒫_{\overline{S}/k}`$. So the assertion follows using the short exact sequence (2.3.1) for $`S^{}`$ and $`C^{}`$ (and replacing $`k`$ if necessary).

If $`r>2`$, we may assume Grothendieck’s generalized Hodge conjecture, and the ‘coniveau’ filtration $`N`$ coincides with the filtration by the level of Hodge structure. If $`S^{}`$ is a sufficiently small open affine subvarieties of $`\overline{S}`$, then

$$W_nH^n(S^{}/k,)=H^n(\overline{S}/k,)/N^1H^n(\overline{S}/k,),$$

and similarly for $`C^{}`$. By the weak Lefschetz theorem, the restriction morphism

$$H^n(\overline{S}/k,)H^n(\overline{C}/k,)$$

is injective, and splits by semisimplicity.

Assume that the pull-back of $`\xi _1`$ by $`C^{}S^{}`$ vanishes. Then, using the long exact sequence associated to (2.3.1), we see that $`\xi _1`$ factors through a direct factor of $`H`$ (or equivalently, of $`H^{2pr}(X/k,))`$ with level $`<n`$, because $`\text{Gr}_{n+1}^WH^n(C^{}/k,)`$ has level $`<n`$. By the Hodge conjecture there exists a smooth proper $`k`$-variety $`Y`$ of pure dimension $`r2`$ together with a correspondence $`\mathrm{\Gamma }\text{CH}^{p1}(Y\times _kX)_{}`$ such that the image of

$$\mathrm{\Gamma }_{}:H^{r2}(Y/k,)H^{2pr}(X/k,)(pr+1)$$

coincides with $`N^{pr+1}H^{2pr}(X/k,)(pr+1)`$ (i.e. the maximal subobject with level $`r2)`$. We have also a correspondence $`\mathrm{\Gamma }^{}\text{CH}^{dimXp+r1}(X\times _kY)_{}`$ such that the restriction of $`\mathrm{\Gamma }_{}\mathrm{\Gamma }_{}^{}`$ to $`\text{Im}\mathrm{\Gamma }_{}H^{2pr}(X/k,)`$ is the identity. So we may replace $`\zeta `$ with $`\mathrm{\Gamma }_{}\mathrm{\Gamma }_{}^{}\zeta `$ to show the vanishing of $`\xi _1`$. Here $`\zeta `$ is extended to $`X\times _k\overline{S}`$ by taking the closure, and the correspondences preserve the filtration $`\tau `$ because they induce morphisms of complexes $`K_{}(X/k)`$, see . Since $`\mathrm{\Gamma }^{}`$ induces

$$\mathrm{\Gamma }_{}^{}:\text{CH}^p(X\times _k\overline{S})\text{CH}^{r1}(Y\times _k\overline{S}),$$

we see that $`\text{supp}\mathrm{\Gamma }_{}^{}\zeta Y\times _kZ`$ with $`Z`$ a divisor on $`\overline{S}`$, because $`r1>dimY`$. So we get the assertion, because $`\text{supp}\mathrm{\Gamma }_{}\mathrm{\Gamma }_{}^{}\zeta X\times _kZ`$.

Now we may assume further $`\xi _1=0`$, i.e. $`\text{Gr}_{F_L}^rcl(\zeta )F_L^2\text{Gr}_{F_L}^r`$. If $`r>2`$, we have $`\text{Gr}_{F_L}^rcl(\zeta )=0`$ by the hypothesis on the coincidence of the two filtrations, because $`F_L^2\text{Gr}_{F_L}^r=0`$ for $`=\text{MHS}`$ and the filtrations $`F_{}`$ and $`F_{}^{}`$ in (1.4) are functorial for $``$. So we may assume $`r=2`$, since the case $`r=1`$ is trivial by the vanishing of $`H^{r2}(S^{}/k,)`$. Then $`\text{Gr}_{F_L}^rcl(\zeta )`$ induces

$$\xi _2\text{Ext}_{}^2(,H^{2p2}(X/k,)H^0(S^{}/k,)(p)),$$

because $`d_2:E_2^{m,1}E_2^{m+2,0}`$ vanishes in (1.3.2) (replacing $`k`$ if necessary) where $`m=2p2,j=p`$. Indeed, $`H^0(S^{}/k,)=`$ is a direct factor of $`K_{}(S^{}/k)`$ by choosing a $`k`$-valued point $`x`$ of $`S^{}`$, because we have $`K_{}(S^{}/k)`$ by the structure morphism and $`x`$. In this case, the assertion is clear because $`H^0(S^{}/k,)=H^0(C^{}/k,)=`$ (replacing $`k`$ if necessary). Thus we have verified all the cases, because $`\text{Gr}_{F_L}^rcl(\zeta )=0`$ if $`\xi _2=0`$ and $`r=2`$. This completes the proof of Theorem (0.3).

2.5. Remarks. (i) It is conjectured that the filtration $`F_{}`$ is separated, and gives the conjectural “motivic” filtration of Beilinson  and Bloch . This depends on the injectivity of the Abel-Jacobi map for smooth projective $`k`$-varieties, which is also a conjecture of Beilinson , see also , , , , etc. It is expected that the filtration $`F_{}`$ does not depend on the choice of $``$, and coincides with Murre’s (conjectural) filtration $`F_{\text{Mur}}`$ . Indeed, we have

$$F_{\text{Mur}}F_{}\text{and}F_{\text{Mur}}=F_{}mod_iF_{}^i,$$
$`(\mathrm{2.5.1})`$
see . The existence of $`F_{\text{Mur}}`$ can be deduced from the separatedness of the filtration $`F_{}`$ assuming the algebraicity of the Künneth components of the diagonal, see . The separatedness of $`F_{}`$ is reduced to the above conjecture of Beilinson on the Abel-Jacobi map for $`k`$-varieties, assuming the Hodge conjecture in the case the codimension of cycles is more than $`2`$.

(ii) We have $`\text{Gr}_F_{}^r\text{CH}^p(X_{})_{}=0`$ for $`r>p`$. If $`=\text{MHS}`$ or $`\text{MHS}_k`$, then $`\text{Gr}_F_{}^r\text{CH}^p(X_K)_{}=0`$ for $`r>\text{tr deg}K/k+1`$. These follow from the vanishing of $`H^i(S_{},)`$ for a smooth affine variety $`S`$ and $`i>dimS`$, together with the compatibility of the cycle map with the pull-back by a closed embedding (and the vanishing of higher extension groups). These assertions have been shown by M. Green and P. Griffiths  for their filtration, assuming the above conjecture of Beilinson and Grothendieck’s generalized Hodge conjecture. Note that these conjectures imply also that the filtration is separated and ends at the $`p`$-th step.

(iii) Restricted to the subgroup $`\text{CH}_{\text{alg}}^p(X)_{}`$ consisting of cycles algebraically equivalent to $`0`$, the kernel of the Abel-Jacobi map coincides with $`F_{}^2\text{CH}_{\text{alg}}^p(X_{})_{}`$, see , 3.9. Indeed, for a curve $`C`$ and a correspondence $`\mathrm{\Gamma }\text{CH}^p(C\times X)_{}`$, we have a decomposition $`H^1(C,)=\text{Im}\mathrm{\Gamma }_{}\text{Ker}\mathrm{\Gamma }_{}`$ induced by idempotents of $`\text{CH}^1(C\times C)_{}`$, where $`\mathrm{\Gamma }_{}:H^1(C,)H^{2p1}(X,)(p1)`$. By a similar argument, the kernel of the usual Abel-Jacobi map coincides with that of the $`l`$-adic Abel-Jacobi map on $`\text{CH}_{\text{alg}}^p(X)_{}`$ (because we have the injectivity in the divisor case using the Kummer sequence).

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text:
# Moment equations for chemical reactions on interstellar dust grains

## 1 Introduction

The chemistry of interstellar clouds consists of reactions taking place in the gas phase as well as on the surfaces of dust grains (Hartquist & Williams 1995). Reactions that take place on dust grain surfaces include the formation of molecular hydrogen as well as reaction networks producing ice mantles and various organic molecules. The formation of H2 on dust grain surfaces is a process of fundamental importance due to the fact that H2 cannot form in the gas phase efficiently enough to account for its observed abundance (Gould & Salpeter 1963; Hollenbach & Salpeter 1970, 1971; Hollenbach et al. 1971). Molecular hydrogen plays a crucial role in gravitational collapse and star formation by absorbing energetic photons and radiating the energy in the infrared, to which the cloud is more transparent, thus cooling it and enabling further collapse. Furthermore, H2 molecules are a necessary component for the initiation of chemical reaction networks that give rise to the chemical complexity observed in interstellar clouds. Therefore, the process of H2 formation has attracted the attention of both theorists (Williams 1968; Smoluchowski 1981, 1983; Aronowitz & Chang 1985; Duley & Williams 1986; Pirronello & Avera 1988; Sandford & Allamandola 1993; Takahashi et al. 1999) and experimentalists (Brackmann 1961; Schutte 1976; Pirronello et al. 1997a ; Pirronello et al. 1997b ; Pirronello et al. 1999; Manico et al. 2001).

The computational modeling of chemical reaction networks on dust grains in the interstellar medium is typically done using rate equation models (Pickles & Williams 1977; d’Hendecourt 1985; Brown 1990; Brown & Charnley 1990; Hasegawa et al. 1992; Hasegawa & Herbst 1993a ; Hasegawa & Herbst 1993b ; Caselli et al. 1993; Willacy & Williams 1993; Shalabiea & Greenberg 1994). These models consist of coupled ordinary differential equations that provide the time derivatives of the densities of the species involved. Integration of these equations provides the time evolution of the densities. As long as the grains are not too small and the flux is not too low, the mean-field approximation applies. In this case, rate equations are an ideal tool for the simulation of surface reactions, due to their high computational efficiency. However, in the limit of very small grains under very low flux, rate equations are not always valid. This is because they take into account only average densities and ignore the fluctuations as well as the discrete nature of the populations of the atomic and molecular species (Tielens 1995; Charnley et al. 1997; Caselli et al. 1998; Shalabiea et al. 1998; Stantcheva et al. 2001). These features become significant in the limit of small grains and low incoming flux, typically encountered in diffuse interstellar clouds where hydrogen recombination as well as various other grain surface reactions take place. For example, as the number of H atoms on a grain fluctuates in the range of 0, 1 or 2, the H2 formation rate cannot be obtained from the average number alone. This can be easily understood, since the recombination process requires at least two H atoms simultaneously on the surface.

Recently, a master equation approach was proposed, that is suitable for the simulation of chemical reactions on microscopic grains (Biham et al. 2001; Green et al. 2001; Biham & Lipshtat 2002). It takes into account both the discrete nature of the H atoms as well as the fluctuations. In the case of hydrogen recombination, its dynamical variables are the probabilities $`P_\mathrm{H}(N_\mathrm{H})`$ that there are $`N_\mathrm{H}`$ atoms on the grain at time $`t`$. The time derivatives $`\dot{P}_\mathrm{H}(N_\mathrm{H})`$, $`N_\mathrm{H}=0,1,2,\mathrm{}`$ are expressed in terms of the adsorption, reaction and desorption terms. The master equation provides the time evolution of $`P_\mathrm{H}(N_\mathrm{H})`$, $`N_\mathrm{H}=0,1,2,\mathrm{}`$, from which the recombination rate can be calculated. The master equation approach has been applied to the study of reaction networks involving multiple species (Stantcheva et al. 2002; Stantcheva & Herbst 2002). Since the state of the system is given by the set of number densities of all species, the number of equations quickly increases with the number of reactive species. Therefore, suitable cutoffs should be imposed in order to keep the number of equations at a tractable level. A Monte Carlo approach based on the master equation was also proposed Charnley (2001), and applied for reaction networks involving multiple species (Stantcheva & Herbst 2002).

In this paper we present a set of moment equations that can be derived from the master equation, and use it to calculate of the rate of molecular hydrogen formation on small grains. In the moment equations, the time derivatives of the moments $`N_\mathrm{H}^k`$, $`k=1,2,\mathrm{}`$, of the distribution $`P_\mathrm{H}(N_\mathrm{H})`$ are expressed in terms of $`N_\mathrm{H}`$, $`N_\mathrm{H}^2`$, $`\mathrm{}`$, $`N_\mathrm{H}^{k+1}`$. To simulate the moment equations we impose a cutoff at a suitable value of $`k`$, giving rise to $`k`$ coupled linear differential equations. With such cutoffs, the moment equations can be used efficiently to calculate the formation rate of molecular hydrogen for both steady state and time dependent conditions. Furthermore, they provide a useful asymptotic expression for the rate of molecular hydrogen formation in the limit of very small grains. This expression can be used in order to integrate the H2 production rate over the grain-size distribution in an interstellar cloud Mathis (1977); Draine (1985, 1985); Mathis (1990, 1996); Weingartner (2001); Cox (2002), and obtain the total production rate per unit volume of the cloud.

In the case of complex reaction networks involving multiple species, the number of moment equations quickly increases as the number of reactive species grows. Furthermore, the higher moments of the distribution are large and cannot be neglected. Thus, setting up the cutoffs in order to limit the number of equations is complicated and tends to introduce significant errors. As a result, for the case of multiple species we have not been able to develop an effective computational framework based on the moment equations. Here we present the set of moment equations for two species, such as hydrogen and oxygen, where the moments take the form $`N_\mathrm{H}^kN_\mathrm{O}^{\mathrm{}}`$, $`k,l=0,1,2,\mathrm{}`$, and discuss the approximations that may be used in order to set suitable cutoffs in these equations. In spite of these difficulties, the moment equation approach has some advantages that justify further attempts to develop it for the case of multiple species. One advantage is that the moment equations are a direct generalization of the rate equations and resemble their structure. One may thus expect that they will be suitable for incorporation into models of interstellar chemistry based on rate equations. Another advantage is that in this approach, the moments, which quantify the production rate of molecules, are directly calculated unlike the case of the master equation where the calculation of moments requires further processing.

The paper is organized as follows. In Sect. 2 we consider reactions involving a single atomic specie, focusing on the case of hydrogen recombination. In Sect. 3 we consider reactions involving two atomic species, such as hydrogen and oxygen. In each of these Sections we briefly describe the rate equations and master equation for the system under study and then introduce and analyze the moment equations. The results are discussed and summarized in Sect. 4.

## 2 Hydrogen recombination

Consider a diffuse interstellar cloud dominated by a density $`\rho _\mathrm{H}`$ (cm-3) of H atoms, and includes some density of dust grains. The typical velocity $`v_\mathrm{H}`$ (cm s-1) of H atoms in the gas phase is given by

$$v_\mathrm{H}=\sqrt{\frac{8}{\pi }\frac{k_BT_{\mathrm{gas}}}{m_H}},$$
(1)
where $`m_H=1.6710^{24}`$ (gram) is the mass of an H atom and $`T_{\mathrm{gas}}`$ is the gas temperature (Landau & Lifshitz 1980). To evaluate the flux of atoms onto grain surfaces we will assume, for simplicity, that the grains are spherical with a radius $`r`$ (cm). The cross section of a grain is $`\sigma =\pi r^2`$ and its surface area is $`4\sigma `$. The number of adsorption sites on a grain is denoted by $`S`$. The flux $`F_\mathrm{H}`$ (atoms s-1) of H atoms onto the surface of a single grain is given by $`F_\mathrm{H}=\rho _\mathrm{H}v_\mathrm{H}\sigma `$. This flux can also be expressed according to $`F_\mathrm{H}=f_\mathrm{H}S`$, where $`f_\mathrm{H}`$ (ML s-1) is given by $`f_\mathrm{H}=\rho _\mathrm{H}v_\mathrm{H}/(4s)`$, and $`s`$ (sites cm-2) is the density of adsorption sites on the surface. The H atoms stick to the surface and hop as random walkers between adjacent sites until they either desorb as atoms or recombine into molecules. The desorption rate of an H atom on the surface is

$$W_\mathrm{H}=\nu \mathrm{exp}(E_1/k_BT),$$
(2)
where $`\nu `$ is the attempt rate (typically assumed to be $`10^{12}`$ s-1), $`E_1`$ is the activation energy barrier for desorption of an H atom and $`T`$ is the surface temperature. The hopping rate of an H atoms is

$$a_\mathrm{H}=\nu \mathrm{exp}(E_0/k_BT),$$
(3)
where $`E_0`$ is the activation energy barrier for H diffusion. Here we assume that diffusion occurs only by thermal hopping, in agreement with recent experimental results (Katz et al. 1999). Throughout this paper we use the parameters obtained experimentally for amorphous carbon, namely the activation energies are $`E_0=44.0`$ meV and $`E_1=56.7`$ meV (Katz et al. 1999), and the density of adsorption sites on the surface is $`s5\times 10^{13}`$ (sites cm-2) (Biham et al. 2001). For the density of hydrogen atoms in the gas phase we take $`\rho _\mathrm{H}=10`$ (atoms cm-3). The gas temperature is taken as $`T_{\mathrm{gas}}=90`$ K, thus $`v_H=1.37\times 10^5`$ (cm s-1). These are typical values for diffuse interstellar clouds.

The number of H atoms on the grain is denoted by $`N_\mathrm{H}`$ and its expectation value under the given conditions is denoted by $`N_\mathrm{H}`$. The rate $`A_\mathrm{H}=a_\mathrm{H}/S`$ is approximately the inverse of the time $`t_s`$ required for an atom to visit nearly all the adsorption sites on the grain surface. This is due to the fact that in two dimensions the number of distinct sites visited by a random walker is linearly proportional to the number of steps, up to a logarithmic correction (Montroll & Weiss 1965).

### 2.1 Rate equation

The rate equation describing H2 formation on dust grain surfaces takes the form

$$\frac{dN_\mathrm{H}}{dt}=F_\mathrm{H}W_\mathrm{H}N_\mathrm{H}2A_\mathrm{H}N_\mathrm{H}^2.$$
(4)
The first term on the right hand side describes the flux of H atoms, the second term describes the desorption of H atoms and the third term describes the diffusion and recombination. Here we assume, for simplicity, that all H2 molecules dosorb from the surface upon formation. The production rate $`R_{\mathrm{H}_2}^{\mathrm{grain}}`$ (molecules s-1) of H2 molecules from a single grain is given by

$$R_{\mathrm{H}_2}^{\mathrm{grain}}=A_\mathrm{H}N_\mathrm{H}^2.$$
(5)
As long as $`N_\mathrm{H}1`$ Eq. (5) provides a very good evaluation of the H2 formation rate. However, for very small grains and low flux, for which $`N_\mathrm{H}1`$ or less, this mean-field approach fails, and tends to overestimate the H2 production. This is because the rate equation does not take into account the discrete nature of the population of H atoms, and the fact that it takes at least two atoms on the surface simultaneously to enable recombination. In this limit, the master equation approach is needed in order to evaluate the H2 formation rate.

### 2.2 Master equation

We will now describe the master equation for H2 formation on small interstellar grains, exposed to a flux $`F_\mathrm{H}`$ of H atoms. At any given time the number of H atoms adsorbed on the grain may be $`N_\mathrm{H}=0,1,2,\mathrm{}`$, and the probability that there are $`N_\mathrm{H}`$ hydrogen atoms on a grain is given by $`P_\mathrm{H}(N_\mathrm{H})`$, where

$$\underset{N_\mathrm{H}=0}{\overset{\mathrm{}}{}}P_\mathrm{H}(N_\mathrm{H})=1.$$
(6)
The time derivatives of these probabilities, $`\dot{P}_\mathrm{H}(N_\mathrm{H})`$, are given by

$`\dot{P}_\mathrm{H}(0)`$ $`=`$ $`F_\mathrm{H}P_\mathrm{H}(0)+W_\mathrm{H}P_\mathrm{H}(1)+21A_\mathrm{H}P_\mathrm{H}(2)`$
$`\dot{P}_\mathrm{H}(1)`$ $`=`$ $`F_\mathrm{H}\left[P_\mathrm{H}(0)P_\mathrm{H}(1)\right]`$
$`+`$ $`W_\mathrm{H}\left[2P_\mathrm{H}(2)P_\mathrm{H}(1)\right]+32A_\mathrm{H}P_\mathrm{H}(3)`$
$`\mathrm{}`$
$`\dot{P}_\mathrm{H}(N_\mathrm{H})`$ $`=`$ $`F_\mathrm{H}\left[P_\mathrm{H}(N_\mathrm{H}1)P_\mathrm{H}(N_\mathrm{H})\right]`$
$`+`$ $`W_\mathrm{H}\left[(N_\mathrm{H}+1)P_\mathrm{H}(N_\mathrm{H}+1)N_\mathrm{H}P_\mathrm{H}(N_\mathrm{H})\right]`$
$`+`$ $`A_\mathrm{H}[(N_\mathrm{H}+2)(N_\mathrm{H}+1)P_\mathrm{H}(N_\mathrm{H}+2)`$
$``$ $`N_\mathrm{H}(N_\mathrm{H}1)P_\mathrm{H}(N_\mathrm{H})].`$
$`\mathrm{}`$
Each of these equations includes three terms. The first term describes the effect of the incoming flux $`F_H`$ on the probabilities. The probability $`P_\mathrm{H}(N_\mathrm{H})`$ increases when an H atom is adsorbed on a grain that already has $`N_\mathrm{H}1`$ adsorbed atoms \[at a rate of $`F_\mathrm{H}P_\mathrm{H}(N_\mathrm{H}1)`$\], and decreases when a new atom is adsorbed on a grain with $`N_\mathrm{H}`$ atoms on it \[at a rate of $`F_\mathrm{H}P_\mathrm{H}(N_\mathrm{H})`$\]. The second term includes the effect of desorption. An H atom that is desorbed from a grain with $`N_\mathrm{H}`$ atoms, decreases the probability $`P_\mathrm{H}(N_\mathrm{H})`$ \[at a rate of $`N_\mathrm{H}W_\mathrm{H}P_\mathrm{H}(N_\mathrm{H})`$\], and increases the probability $`P_\mathrm{H}(N_\mathrm{H}1)`$ at the same rate. The third term describes the effect of recombination on the number of adsrobed H atoms. The production of one molecule reduces this number from $`N_\mathrm{H}`$ to $`N_\mathrm{H}2`$. For one pair of H atoms the recombination rate is proportional to the sweeping rate $`A_\mathrm{H}`$ multiplied by 2 since both atoms are mobile simultaneously. This rate is multiplied by the number of possible pairs of atoms, namely $`N_\mathrm{H}(N_\mathrm{H}1)/2`$. Note that the equations for $`\dot{P}_\mathrm{H}(0)`$ and $`\dot{P}_\mathrm{H}(1)`$ do not include all the terms, because at least one H atom is required for desorption to occur and at least two for recombination. The rate of formation of H2 molecules, $`R_{\mathrm{H}_2}^{\mathrm{grain}}`$ (molecules s-1), on the surface of a single grain is thus given by

$$R_{\mathrm{H}_2}^{\mathrm{grain}}=A_\mathrm{H}[N_\mathrm{H}^2N_\mathrm{H}]$$
(8)
where

$$N_\mathrm{H}^k=\underset{N_\mathrm{H}=0}{\overset{\mathrm{}}{}}N_\mathrm{H}^kP_\mathrm{H}(N_\mathrm{H}).$$
(9)
is the $`k`$th moment of the distribution.

The time dependence of $`R_{\mathrm{H}_2}^{\mathrm{grain}}`$ can be obtained by numerically integrating Eqs. (2.2) using a standard Runge-Kutta stepper. For the case of steady state, namely $`\dot{P}_\mathrm{H}(N_\mathrm{H})=0`$ for all $`N_\mathrm{H}`$, an analytical solution for $`P_\mathrm{H}(N_\mathrm{H})`$ is available, given in terms of $`A_\mathrm{H}/W_\mathrm{H}`$ and $`W_\mathrm{H}/F_\mathrm{H}`$ (Green et al. 2001; Biham & Lipshtat 2002).

### 2.3 Moment equations

By expanding the time derivatives $`\dot{N}_\mathrm{H}^k`$, $`k=1,2,\mathrm{}`$, using Eq. (9) and inserting the expression for $`\dot{P}_\mathrm{H}(N_\mathrm{H})`$ from the master equation (2.2), one obtains the moment equations:

$`{\displaystyle \frac{dN_\mathrm{H}}{dt}}`$ $`=`$ $`F_\mathrm{H}+(W_\mathrm{H}+2A_\mathrm{H})N_\mathrm{H}2A_\mathrm{H}N_\mathrm{H}^2`$
$`{\displaystyle \frac{dN_\mathrm{H}^2}{dt}}`$ $`=`$ $`F_\mathrm{H}+(2F_\mathrm{H}+W_\mathrm{H}4A_\mathrm{H})N_\mathrm{H}`$
$`+`$ $`(8A_\mathrm{H}2W_\mathrm{H})N_\mathrm{H}^24A_\mathrm{H}N_\mathrm{H}^3`$
$`{\displaystyle \frac{dN_\mathrm{H}^3}{dt}}`$ $`=`$ $`F_\mathrm{H}+(3F_\mathrm{H}W_\mathrm{H}+8A_\mathrm{H})N_\mathrm{H}`$
$`+`$ $`(3F_\mathrm{H}+3W_\mathrm{H}20A_\mathrm{H})N_\mathrm{H}^2`$
$`+`$ $`(18A_\mathrm{H}3W_\mathrm{H})N_\mathrm{H}^36A_\mathrm{H}N_\mathrm{H}^4`$
$`\mathrm{}`$
$`{\displaystyle \frac{dN_\mathrm{H}^k}{dt}}`$ $`=`$ $`F_\mathrm{H}(1+N_\mathrm{H})^kN_\mathrm{H}^k`$
$`+`$ $`W_\mathrm{H}N_\mathrm{H}[(N_\mathrm{H}1)^kN_\mathrm{H}^k]`$
$`+`$ $`A_\mathrm{H}N_\mathrm{H}(N_\mathrm{H}1)[(N_\mathrm{H}2)^kN_\mathrm{H}^k].`$
$`\mathrm{}`$ (10)
This is a set of coupled differential equations, that are linear in the moments $`N_\mathrm{H}^k`$. The equation for the $`k`$th moment depends on all the moments up the the $`(k+1)`$th order. A numerical integration of these equations would provide the values of these moments at any given time. The H2 production rate, that depends only on the first and second moments, could then be obtained. However, the difficulty is that we need to truncate this set of equations, say after the equation of the $`k`$th moment. The $`(k+1)`$th moment appears in this equation and we end up with more unknowns than equations. The $`(k+1)`$th moment should then be approximated as a function of the first $`k`$ moments. The approximation should be examined carefully since $`N_\mathrm{H}^{k+1}`$ is not a small quantity (unlike the case when the master equation is truncated). In fact, due to the discreteness of $`N_\mathrm{H}`$, the moments increase monotonically with their order, namely $`N_\mathrm{H}^kN_\mathrm{H}^{k+1}`$, $`k=1,2,\mathrm{}`$ (and the $``$ symbol is replaced by the $`<`$ symbol if $`P_\mathrm{H}(N_\mathrm{H})>0`$ for at least one value of $`N_\mathrm{H}>1`$).

#### 2.3.1 Setting the cutoffs

Consider the case in which only up to $`k`$ hydrogen atoms are allowed to reside simultaneously on the surface of a grain. The moments of the resulting truncated distribution $`P_\mathrm{H}(N_\mathrm{H})`$ will be

$`N_\mathrm{H}^1`$ $`=`$ $`P_\mathrm{H}(1)+2P_\mathrm{H}(2)+\mathrm{}+kP_\mathrm{H}(k)`$
$`N_\mathrm{H}^2`$ $`=`$ $`P_\mathrm{H}(1)+4P_\mathrm{H}(2)+\mathrm{}+k^2P_\mathrm{H}(k)`$
$`\mathrm{}`$
$`N_\mathrm{H}^k`$ $`=`$ $`P_\mathrm{H}(1)+2^kP_\mathrm{H}(2)+\mathrm{}+k^kP_\mathrm{H}(k)`$
$`N_\mathrm{H}^{k+1}`$ $`=`$ $`P_\mathrm{H}(1)+2^{k+1}P_\mathrm{H}(2)+\mathrm{}+k^{k+1}P_\mathrm{H}(k).`$ (11)
The first $`k`$ equations in Eqs. (11) can be used in order to express $`P_\mathrm{H}(1)`$ ,$`\mathrm{}`$, $`P_\mathrm{H}(k)`$ in terms of $`N_\mathrm{H}^1`$, $`\mathrm{}`$, $`N_\mathrm{H}^k`$. The results can then be plugged into the $`(k+1)`$th equation in Eqs. (10), thus expressing $`N_\mathrm{H}^{k+1}`$ in terms of the first $`k`$ moments. For example, in the case of $`k=2`$ we obtain the third moment as a function of the first two:

$`N_\mathrm{H}^3=3N_\mathrm{H}^22N_\mathrm{H}^1.`$ (12)
Similarly, when $`P_\mathrm{H}(N_\mathrm{H})`$ is truncated after $`k=3`$ or $`k=4`$ we obtain

$$N_\mathrm{H}^4=6N_\mathrm{H}^111N_\mathrm{H}^2+6N_\mathrm{H}^3$$
(13)
and

$$N_\mathrm{H}^5=24N_\mathrm{H}^1+50N_\mathrm{H}^235N_\mathrm{H}^3+10N_\mathrm{H}^4,$$
(14)
respectively. In general, when up to $`k`$ hydrogen atoms are allowed to reside on a grain the $`(k+1)`$th moment, $`N_\mathrm{H}^{k+1}`$, can be expressed as a linear combination of the first $`k`$ moments according to

$$N_\mathrm{H}^{k+1}=\underset{n=1}{\overset{k}{}}C_{k+1}(n)N_\mathrm{H}^n.$$
(15)
The coefficients $`C_{k+1}(n)`$ are obtained from the solution of a set of linear algebraic equations, that can be expressed in a matrix form as

$$VC=v.$$
(16)
The matrix $`V`$ is the Vandermonde matrix of size $`k\times k`$, namely, $`V_{mn}=m^n`$, where $`m,n=1,2,\mathrm{},k`$, and the vector $`v`$ consists of $`v_m=m^{k+1}`$, $`m=1,2,\mathrm{},k`$. The desired coefficients are the elements of the vector $`C=[C_{k+1}(1),\mathrm{},C_{k+1}(k)]`$. The coefficient $`C_{k+1}(n)`$ turn out to be equal to the coefficient of $`x^n`$ in the polynomial Bender et al. (2002)

$$Q_k(x)=\underset{j=0}{\overset{k}{}}(xj).$$
(17)
Having an expression for $`N_\mathrm{H}^{k+1}`$ as a linear combination of the first $`k`$ moments, we can now insert it into the last equation in Eq. (10). We then obtain a set of $`k`$ coupled linear differential equations for the first $`k`$ moments. This set of equations can be simulated using a standard Runge-Kutta or any other stepper routine. A convenient choice of initial condition may be the case of an empty grain. In this case the moment equations are initiated with $`N_\mathrm{H}^n=0`$ for all $`n1`$ (while the master equation is initiated with $`P_\mathrm{H}(0)=1`$ and $`P_\mathrm{H}(n)=0`$ for $`n1`$).

#### 2.3.2 Calculations and results

To determine the desirable value of the cutoff $`k`$, for steady state calculations using the moment equations, it is useful to first calculate $`N_\mathrm{H}`$ using the rate equations \[Eq. (4)\] for the same parameters used in the moment equations. We found that a suitable choice for the truncation is $`k=N_\mathrm{H}+C`$ where $`x`$ is the smallest integer which is larger than $`x`$. The parameter $`C`$ is determined such that a sufficient number of equations are included to provide a good agreement with the master equation. In all the calculations presented here we used $`C=1.2`$.

We have used the moment equations to simulate the hydrogen recombination process on a grain under steady state conditions, and compared the results with those of the rate equations and the master equation. The surface parameters used are of amorphous carbon. The gas density and temperature are those specified above, and the surface temperature is $`T=18`$ K.

The number of H atoms on the grain is shown in Fig. 1(a) as a function of the number of adsorption sites, $`S`$, using the rate equations (dashed line), master equation ($``$) and moment equations (solid line). The production rate of H2 molecules on the surface of a single grain is shown in Fig. 1(b) as a function of $`S`$. The results of the rate equations (dashed line) are simply linearly proportional to $`S`$. For large enough grains the results of the rate equations coincide with those of the master equation ($``$) and the moments equations (solid line). For small grains, the results of the moment equations are in perfect agreement with the master equation, while the rate equations greatly over-estimate the production rate. In the simulations of the moment equations, the cutoff was determined according the the procedure specified above. The number of equations used in each range of grain sizes is specified. Note that using this procedure we obtain a perfect agreement between the moment equations and the master equation for the entire range of grain sizes. Results are also shown for the master equation with cutoffs after the third equation ($`\times `$) and after the fifth equation ($`+`$). It is shown that while the sets of two, three and four moment equations provide a perfect agreement with the complete master equation in the specified domains, the master equation with cutoffs (including at least as many equations) exhibits significant deviations.

In the limit of very small grains, only two moment equations are needed in order to obtain perfect agreement with the master equation. These equation are derived from the first two moment equations in Eqs. (10) and the cutoff condition given in Eq. (12). They take the form

$`{\displaystyle \frac{dN_\mathrm{H}}{dt}}`$ $`=`$ $`F_\mathrm{H}+(2A_\mathrm{H}W_\mathrm{H})N_\mathrm{H}2A_\mathrm{H}N_\mathrm{H}^2`$
$`{\displaystyle \frac{dN_\mathrm{H}^2}{dt}}`$ $`=`$ $`F_\mathrm{H}+(2F_\mathrm{H}+W_\mathrm{H}+4A_\mathrm{H})N_\mathrm{H}(4A_\mathrm{H}+2W_\mathrm{H})N_\mathrm{H}^2.`$ (18)
We find that these equations are dynamically stable and can be used for time-dependent simulations. In Fig. 2 we present the results of time-dependent simulations using Eqs. (18) for a large grain ($`S=62,831`$ sites) and for a small grain ($`S=628`$ sites). The expectation value $`N_\mathrm{H}`$ vs. time is shown in Fig. 2(a), and the production rate $`R_{\mathrm{H}_2}^{\mathrm{grain}}`$ of molecular hydrogen is shown in Fig. 2(b). The initial condition is of an empty grain surface, while the surface parameters, the temperature and the flux are identical to those used in Fig. 1. For the large grain, it is found that the moment equations, master equation and the rate equation are all in perfect agreement even during the transient time. For the small grain, the set of two moment equations is in perfect agreement with the complete master equation, while the rate equation deviates significantly. For steady state conditions, Eqs. (18) can be solved exactly, giving rise to

$`N_\mathrm{H}`$ $`=`$ $`{\displaystyle \frac{F_\mathrm{H}(A_\mathrm{H}+W_\mathrm{H})}{2A_\mathrm{H}F_\mathrm{H}+W_\mathrm{H}A_\mathrm{H}+W_\mathrm{H}^2}}`$
$`N_\mathrm{H}^2`$ $`=`$ $`{\displaystyle \frac{F_\mathrm{H}(F_\mathrm{H}+A_\mathrm{H}+W_\mathrm{H})}{2A_\mathrm{H}F_\mathrm{H}+W_\mathrm{H}A_\mathrm{H}+W_\mathrm{H}^2}}.`$ (19)
A simple exact expression for the production rate $`R_{\mathrm{H}_2}^{\mathrm{grain}}`$, of molecular hydrogen, given by Eq. (8), can now be obtained for steady state conditions in the limit of small grains and low flux. It takes the form

$$R_{\mathrm{H}_2}^{\mathrm{grain}}=\frac{f_\mathrm{H}^2}{W_\mathrm{H}}\left[\frac{S^2}{1+\frac{S}{a_\mathrm{H}/W_\mathrm{H}}+2\frac{S}{W_\mathrm{H}/f_\mathrm{H}}}\right].$$
(20)
We observe that, as long as $`S`$ is larger than both $`s_{\mathrm{visit}}=a_\mathrm{H}/W_\mathrm{H}`$ (the number of sites that an H atom typically visits before it desorbs) and $`s_{\mathrm{vacant}}=W_\mathrm{H}/f_\mathrm{H}`$ (the typical number of vacant sites per adsorbed H atom), the production rate is linearly proportional to $`S`$, and the grain size does not play any special role Biham & Lipshtat (2002). In the case of small grains for which $`S`$ is smaller than both $`s_{\mathrm{visit}}`$ and $`s_{\mathrm{vacant}}`$ the production rate is reduced and becomes proportional to $`S^2`$. The production efficiency $`\eta (S)=2R_{\mathrm{H}_2}^{\mathrm{grain}}/F_\mathrm{H}`$ then takes the form

$$\eta (S)=\frac{2f_\mathrm{H}}{W_\mathrm{H}}\left[\frac{S}{1+\frac{S}{a_\mathrm{H}/W_\mathrm{H}}+2\frac{S}{W_\mathrm{H}/f_\mathrm{H}}}\right].$$
(21)
In Fig. 3 we present the production efficiency, given by Eq. (21), as a function of $`S`$ under the same conditions as those used in Fig. 1. For very small grains, namely for $`S<\mathrm{min}\{s_{\mathrm{visit}},s_{\mathrm{vacant}}\}`$, the efficiency $`\eta (S)`$ is linearly proportional to $`S`$, while for $`S>\mathrm{max}\{s_{\mathrm{visit}},s_{\mathrm{vacant}}\}`$ it saturates and coincides with the rate equation result that is independent of $`S`$.

These results can now be used in order to evaluate the total production of molecular hydrogen per unit volume of the cloud from grains of all sizes. Consider a cloud in which the grain size distribution is given by $`\rho _{\mathrm{gr}}(r)`$ (cm-4) in the range $`r_{\mathrm{min}}<r<r_{\mathrm{max}}`$, where $`r_{\mathrm{min}}`$ and $`r_{\mathrm{max}}`$ are the lower and upper cutoffs of the distribution \[here $`\rho _{\mathrm{gr}}(r)dr`$ (cm-3) is the number density of grains of sizes in the range (r,r+dr)\]. The formation rate $`R_{\mathrm{H}_2}`$ (cm-3 s-1 ) of molecular hydrogen in the cloud is given by

$$R_{\mathrm{H}_2}=\rho _\mathrm{H}v_\mathrm{H}_{r_{\mathrm{min}}}^{r_{\mathrm{max}}}\pi r^2\rho _{\mathrm{gr}}(r)\eta (S)𝑑r.$$
(22)
where $`\eta (S)`$ is given by Eq. (21) and $`S=4\pi r^2s`$.

To demonstrate these ideas we will consider a simple example in which the grain size distribution exhibits a power-law behavior of the form

$$\rho _{\mathrm{gr}}(r)=\frac{K}{r^\alpha },$$
(23)
where $`\alpha =3`$. The special property of this distribution is that the total grain mass is equally distributed in the entire range of grain sizes $`r_{min}rr_{max}`$. Unlike the mass, the total surface area of all grains in the size range between $`r`$ and $`r+dr`$, scales like $`r^1`$, namely most of the grain surface area is on the small grains. The prefactor $`K`$ is determined by the condition that the total number density of grains is smaller than $`\rho _\mathrm{H}`$ by a factor of $`10^{12}`$. Under this condition $`K=210^{11}/(r_{min}^2r_{max}^2)`$. In this case the integral can be easily evaluated and the result is

$$R_{\mathrm{H}_2}=\frac{4\pi ^2K\rho _\mathrm{H}v_\mathrm{H}f_\mathrm{H}s}{W_\mathrm{H}B}\mathrm{ln}\left(\frac{Br_{\mathrm{max}}^2+1}{Br_{\mathrm{min}}^2+1}\right)$$
(24)
where $`B=4\pi s[W_\mathrm{H}/a_\mathrm{H}+2f_\mathrm{H}/W_\mathrm{H}]`$. To evaluate the contribution of grains of different sizes to the total production rate of molecular hydrogen, we show in Fig. 4 the differential production rate, given by the integrand in Eq. (22), vs. the grain radius, $`r`$, where $`r_{\mathrm{min}}=2\times 10^7`$ (cm) and $`r_{\mathrm{max}}=1.25\times 10^5`$ (cm). Starting from the limit of large grains, the differential production increases with decreasing grain size due to the larger total surface area of smaller grains. However, below some grain size the recombination efficiency decreases and the differential production rate starts to decrease. We observe that under these conditions the largest contribution comes from extremely small grains of sizes around 20 nm. Observation indicate that the exponent in Eq. (23) is $`\alpha =3.5`$ (see e.g. Weingartner & Draine 2001). Therefore, the contribution of very small grains to molecular hydrogen formation may be even more dominant than in the analysis shown here.

Observations indicate that the temperatures of dust grains in diffuse clouds are typically in the range between 10 - 20 K. The dependence of the molecular hydrogen formation process on the surface temperature of the grains is presented in Fig. 5. The average number of H atoms on the surface of a very small grain of radius $`r=10^6`$ (cm) is shown in Fig. 5(a). The production rate of molecular hydrogen on such grain is shown in Fig. 5(b). The results of the moment equations (solid line) and the master equation ($``$) coincide perfectly, while the rate equations (dashed line) significantly overestimate the production rate for temperatures higher than 16 K. As the temperature increases above $`T=16`$ K, desorption becomes faster and the production rate decreases. Below 16 K the production rate saturates and becomes independent of the temperature within the temperature window of 12 - 16 K. Below $`T=12`$ K the production rate decreases sharply due to the lower mobility of H atoms on the surface Katz et al. (1999).

## 3 Reactions involving two Species

Observations in the past two decades provide evidence that chemical reaction networks on dust grain surfaces go much beyond the production of molecular hydrogen. In particular, ice mantles that consist of H2O and CO, as well as more complex organic molecules, form on grain surfaces.

Here we consider a surface reaction network involving hydrogen and oxygen (Caselli et al. 1998). In this system surface reactions produce H2, O2, OH and H2O molecules. While the hydrogen molecules typically desorb upon formation or shortly later, the heavier species tend to remain on the surface. Some of them, such as OH may then participate in further reactions. However, in the model presented below we assume, for simplicity, that the reaction products do not participate in further chemical reactions (namely, H2O is not produced). In practice, we consider these molecules as if they all desorb from the surface upon formation.

### 3.1 Rate equations

The rate equations that describe the chemical reactions on dust grains in our simplified hydrogen-oxygen system are

$`{\displaystyle \frac{dN_\mathrm{H}}{dt}}`$ $`=`$ $`F_\mathrm{H}W_\mathrm{H}N_\mathrm{H}2A_\mathrm{H}N_\mathrm{H}^2`$
$``$ $`(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
$`{\displaystyle \frac{dN_\mathrm{O}}{dt}}`$ $`=`$ $`F_\mathrm{O}W_\mathrm{O}N_\mathrm{O}2A_\mathrm{O}N_\mathrm{O}^2`$ (25)
$``$ $`(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
where $`N_\mathrm{O}`$ is the number of oxygen atoms on the grain and $`A_\mathrm{O}=a_\mathrm{O}/S`$ is their sweeping rate. Here we denote the density of the O atoms in the gas phase by $`\rho _O`$. Their velocity, $`v_\mathrm{O}`$, is determined by Eq. (1) (replacing $`m_\mathrm{H}`$ by the mass $`m_\mathrm{O}`$ of an oxygen atom) with the same temperature as that of the hydrogen gas. The flux of O atoms adsorbed on the grain surface is given by $`F_\mathrm{O}=\rho _\mathrm{O}v_\mathrm{O}\sigma `$ (atoms s-1). The desorption rate $`W_\mathrm{O}`$ is given by an expression analogous to Eq. (2) with the same $`\nu `$ and with $`E_1`$ replaced by the activation energy for desorption of O atoms. The hopping rate $`a_\mathrm{O}`$ of the O atoms is given by an expression analogous to Eq. (3), with $`E_0`$ replaced by the activation energy for hopping of O atoms.

As long as the grains are not too small and the fluxes are not too low, such that $`N_\mathrm{H}1`$ and $`N_\mathrm{O}1`$ these rate equations evaluate correctly the formation rates of all the reaction products. However, when the typical numbers of H or O atoms on the grain go down to order one, these equations become unsuitable and exhibit significant deviations from the actual production rates.

### 3.2 Master equation

The master equation that describes the hydrogen-oxygen system consists of a two dimensional matrix of equations for the time derivatives of $`P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})`$. It takes the form

$`\dot{P}_{\mathrm{H}\&\mathrm{O}}`$ $`(`$ $`N_\mathrm{H},N_\mathrm{O})=F_\mathrm{H}[P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H}1,N_\mathrm{O})`$
$``$ $`P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})]`$
$`+`$ $`F_\mathrm{O}[P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O}1)`$
$``$ $`P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})]`$
$`+`$ $`W_\mathrm{H}[(N_\mathrm{H}+1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H}+1,N_\mathrm{O})`$
$``$ $`N_\mathrm{H}P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})]`$
$`+`$ $`W_\mathrm{O}[(N_\mathrm{O}+1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O}+1)`$
$``$ $`N_\mathrm{O}P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})]`$
$`+`$ $`A_\mathrm{H}[(N_\mathrm{H}+2)(N_\mathrm{H}+1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H}+2,N_\mathrm{O})`$
$``$ $`N_\mathrm{H}(N_\mathrm{H}1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})]`$
$`+`$ $`A_\mathrm{O}[(N_\mathrm{O}+2)(N_\mathrm{O}+1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O}+2)`$
$``$ $`N_\mathrm{O}(N_\mathrm{O}1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})]`$
$`+`$ $`(A_\mathrm{H}+A_\mathrm{O})`$
$`[`$ $`(N_\mathrm{H}+1)(N_\mathrm{O}+1)P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H}+1,N_\mathrm{O}+1)`$
$``$ $`N_\mathrm{H}N_\mathrm{O}P_{\mathrm{H}\&\mathrm{O}}(N_\mathrm{H},N_\mathrm{O})],`$
where $`N_\mathrm{H},N_\mathrm{O}=0,1,2,\mathrm{}`$. In the equations in which $`N_\mathrm{H}=0,1`$ or $`N_\mathrm{O}=0,1`$, some of the terms vanish. These terms can be easily identified since their initial or final states include a negative number of H or O atoms on the grain.

### 3.3 Moment equations

The moment equations for the hydrogen-oxygen system take the form

$`{\displaystyle \frac{dN_\mathrm{H}}{dt}}`$ $`=`$ $`F_\mathrm{H}+(2A_\mathrm{H}W_\mathrm{H})N_\mathrm{H}2A_\mathrm{H}N_\mathrm{H}^2`$
$``$ $`(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
$`{\displaystyle \frac{dN_\mathrm{O}}{dt}}`$ $`=`$ $`F_\mathrm{O}+(2A_\mathrm{O}W_\mathrm{O})N_\mathrm{O}2A_\mathrm{O}N_\mathrm{O}^2`$
$``$ $`(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
$`{\displaystyle \frac{dN_\mathrm{H}^2}{dt}}`$ $`=`$ $`F_\mathrm{H}+(2F_\mathrm{H}+W_\mathrm{H}4A_\mathrm{H})N_\mathrm{H}`$
$`+`$ $`(2W_\mathrm{H}+8A_\mathrm{H})N_\mathrm{H}^2`$
$``$ $`4A_\mathrm{H}N_\mathrm{H}^3+(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
$``$ $`2(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}^2N_\mathrm{O}`$
$`{\displaystyle \frac{dN_\mathrm{O}^2}{dt}}`$ $`=`$ $`F_\mathrm{O}+(2F_\mathrm{O}+W_\mathrm{O}4A_\mathrm{O})N_\mathrm{O}`$
$`+`$ $`(2W_\mathrm{O}+8A_\mathrm{O})N_\mathrm{O}^2`$
$``$ $`4A_\mathrm{O}N_\mathrm{O}^3+(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
$``$ $`2(A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}^2`$
$`{\displaystyle \frac{dN_\mathrm{H}N_\mathrm{O}}{dt}}`$ $`=`$ $`F_\mathrm{H}N_\mathrm{O}+F_\mathrm{O}N_\mathrm{H}`$ (27)
$`+`$ $`(W_\mathrm{H}W_\mathrm{O}+3A_\mathrm{H}+3A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}`$
$``$ $`(3A_\mathrm{H}+A_\mathrm{O})N_\mathrm{H}^2N_\mathrm{O}`$
$``$ $`(A_\mathrm{H}+3A_\mathrm{O})N_\mathrm{H}N_\mathrm{O}^2.`$
and the production rates of the molecular species are given by

$`R_{\mathrm{H}_2}^{\mathrm{grain}}`$ $`=`$ $`A_\mathrm{H}\left(N_\mathrm{H}^2N_\mathrm{H}\right)`$
$`R_{\mathrm{O}_2}^{\mathrm{grain}}`$ $`=`$ $`A_\mathrm{O}\left(N_\mathrm{O}^2N_\mathrm{O}\right)`$
$`R_{\mathrm{OH}}^{\mathrm{grain}}`$ $`=`$ $`\left(A_\mathrm{H}+A_\mathrm{O}\right)N_\mathrm{H}N_\mathrm{O}.`$ (28)
In the moment equations the time derivative of each moment is expressed as a linear combination of other moments. The set can be extended to include higher moments. However, the number of unknowns (namely moments to be computed) grows faster than the number of equations. In Eqs. (27), consisting of five equations, there are nine unknowns: $`N_\mathrm{H}`$, $`N_\mathrm{O}`$, $`N_\mathrm{H}^2`$, $`N_\mathrm{O}^2`$, $`N_\mathrm{H}^3`$, $`N_\mathrm{O}^3`$, $`N_\mathrm{H}N_\mathrm{O}`$, $`N_\mathrm{H}^2N_\mathrm{O}`$ and $`N_\mathrm{H}N_\mathrm{O}^2`$.

Therefore, in order to solve the moment equations one has to use approximations for four of the unknowns listed above. In principle, these approximations can be obtained using the following properties. The number density of hydrogen in the gas phase is by orders of magnitude higher than that of any other specie, including oxygen. Therefore, $`F_\mathrm{H}F_\mathrm{O}`$. The activation energies for diffusion and desorption of H atoms on the grain surface are much lower than those of heavier atomic species such as oxygen. Therefore, the diffusion of H atoms on the surface is much faster and dominates the chemical activity on the surface. The density of H atoms on the surface is thus primarily controlled by the processes of H2 formation and H desorption. The further reduction of H density due to the formation of OH can be considered as a small correction. We have examined such approximations and found that they do not work very well in practice and that the results deviate significantly from those of the master equation.

## 4 Summary

We have introduced a set of moment equations for the analysis of the formation of molecular hydrogen and other chemical reactions on dust grain surfaces in the interstellar medium. These equations are derived from the master equation that describes these processes. Like the master equation, the moment equations are exact even in the limit of small grains and low flux where the rate equations fail. They take into account the discrete nature of the populations of atomic and molecular species that participate in the reactions. While the master equation is expressed in terms of distributions such as $`P_\mathrm{H}(N_\mathrm{H})`$, $`N_\mathrm{H}=0,1,2\mathrm{}`$, the moment equations are expressed in terms of the moments of these distributions.

We have shown that the moment equation approach is useful for simulations of molecular hydrogen formation. We expect that this approach will make it possible to efficiently calculate the total production rate of molecular hydrogen in diffuse clouds. The results will then be used in order to determine whether the molecular hydrogen formation process studied here is efficient enough to account for the observed abundance of H2. The input required for such calculations includes the surface parameters (obtained from laboratory experiments), the grain size distribution, the density and temperature of the H gas, the grain temperature as well as the dissociation rate of H2 molecules in the gas phase. Since the formation rate of molecular hydrogen is highly sensitive to the grain temperature and size distribution, the accuracy of the results may be limited by the quality of the observational data.

For more complex reaction networks involving multiple species, setting the cutoffs in the moment equations requires certain approximations that introduce significant errors. Therefore, for system that consist of more than a single reactive specie, we currently do not have a useful computational framework based on the moment equations. Potential advantages of the moment equations, justifying further attempts to further develop this approach, include the fact that they are similar in structure to the rate equations, possibly making it easier to incorporate them into models of interstellar chemistry. Moreover, they directly provide the first and second moments, which quantify the production rates of the molecular species involved. This is unlike the master equation in which the moments are calculated from the distribution in a post-processing stage.

###### Acknowledgements.

We thank E. Herbst, V. Pirronello and G. Vidali for helpful discussions and correspondence. This work was supported by the Adler Foundation for Space Research of the Israel Science Foundation.


text:
# 1 Introduction

## 1 Introduction

We consider an exciton, i.e. an electron–hole pair created in a quantum dot (QD) by extremely short optical pulse (Borri 2001, Kikkawa 1988). The rapidly created bare exciton is further dressing with phonons, which results in arising a composite quasiparticle being the coherent mixture of the electron–hole pair and phonons. Its energy is lower than the bare exciton energy. In the case of interaction with only optical phonons this composite particle can be called exciton–polaron in analogy to the Frolich electron–polaron. In a realistic model much weaker deformation effects responsible for the interaction with acoustical phonons are included.

The observation of the exciton dressing with phonons is possible when the dipole coupling with the electromagnetic field is sufficiently strong to preserve a non adiabatic (i.e. rapid) exciton creation (cf. 0.2ps laser pulse in Ref. (Borri 2001)) much faster than dressing with phonons (of ps scale as we will show below). We consider a weakly polar medium for QDs (GaAs) in which the interaction of electrons with longitudinal optical (LO) phonons is dominating in terms of the influence on the quasiparticle energy shift. Much weaker interaction with gap–less longitudinal acoustic (LA) phonons plays an important role in kinematics of the dressing process, being a channel of energy transfer from exciton. In order to determine the limit of decoherence time of the optical excitations in QDs, this LA channel for dressing exciton with LO/LA phonons must be included.

We describe and analyse the dressing and the relaxation of exciton problems in detail for typical self–assembled strain induced InAs/GaAs QDs (Jacak 1998) within the Green function formulation. We model the QD by the parabolic confinement potential.

## 2 Phonon dressing description

In order to investigate the time evolution of the lowest exciton state, we consider the Hamiltonian describing a single electron and a hole interacting with phonons

$`=_e(𝐫_e)+_h(𝐫_h){\displaystyle \frac{e^2}{ϵ_0|𝐫_e𝐫_h|}}+{\displaystyle \underset{𝐤s}{}}\mathrm{}\omega _{𝐤s}b_{𝐤s}^{}b_{𝐤s}{\displaystyle \frac{e}{N^{1/2}}}\left({\displaystyle \frac{2\pi \mathrm{}\mathrm{\Omega }}{\upsilon \stackrel{~}{ϵ}}}\right)^{1/2}{\displaystyle \underset{𝐤}{}}{\displaystyle \frac{1}{k}}`$
$`\times (b_{𝐤o}+b_{𝐤o}^{})(\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_e}\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_h}){\displaystyle \frac{1}{N^{1/2}}}\left({\displaystyle \frac{\mathrm{}}{2Mc_a}}\right)^{1/2}{\displaystyle \underset{𝐤}{}}k^{1/2}(b_{𝐤a}+b_{𝐤a}^{})(\sigma _e\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_e}\sigma _h\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_h}).`$ (1)
Here $`b_{𝐤s}^{}(b_{𝐤s})`$ denote the phonon creation (annihilation) operators, ($`s=o`$ for LO, $`s=a`$ for LA), $`\mathrm{\Omega }`$ denotes the frequency of the zero wave vector LO phonons, $`c_a`$ – the LA phonon frequency, $`\sigma _{e,h}`$ – deformation constants for the electron and hole, $`M`$ – the mass of ions in the elementary cell, $`\upsilon `$ – the elementary cell volume, $`N`$ – the number of cells in crystal, $`\stackrel{~}{ϵ}=(1/ϵ_{\mathrm{}}1/ϵ_0)^1`$ – the effective dielectric constant. The electron (hole) part of the Hamiltonian

$`_i(𝐫_i)={\displaystyle \frac{\mathrm{}^2}{2m_i^{}}}_i^2+{\displaystyle \frac{1}{2}}m_i^{}(\omega _0^i)^2r_i^2+{\displaystyle \frac{1}{2}}m_i^{}(\omega _z^i)^2z_i^2`$ (2)
(where $`i=e,h`$, $`r_i^2=x_i^2+y_i^2`$) contains the vertical and horizontal confinement potentials. There are characteristic confinement sizes $`l_i=\sqrt{\frac{\mathrm{}}{m_i^{}\omega _0^i}}`$, $`l_{iz}=\sqrt{\frac{\mathrm{}}{m_i^{}\omega _z^i}}`$ ($`\omega _0^i\omega _z^i`$). Finding the eigenfunctions $`\mathrm{\Phi }_n(𝐫_e,𝐫_h)`$ of the exciton Hamiltonian

$$_{ex}=_e(𝐫_e)+_h(𝐫_h)\frac{e^2}{ϵ_0|𝐫_e𝐫_h|},$$
(3)
we write the Hamiltonian (1) in the second quantisation representation in the form of the sum of unperturbed and interaction parts

$`={\displaystyle \underset{n}{}}\mathrm{}E_na_n^{}a_n+{\displaystyle \underset{𝐤,s}{}}\mathrm{}\omega _{𝐤s}b_{𝐤s}^{}b_{𝐤s}+{\displaystyle \frac{1}{N^{1/2}}}{\displaystyle \underset{n_1,n_2,𝐤,s}{}}F_s(n_1,n_2,𝐤)a_{n_1}^{}a_{n_2}(b_{𝐤o}+b_{𝐤o}^{}),`$ (4)
where

$`F_o(n_1,n_2,𝐤)={\displaystyle \frac{e}{k}}\left({\displaystyle \frac{2\pi \mathrm{}\mathrm{\Omega }}{\upsilon \stackrel{~}{ϵ}}}\right)^{1/2}{\displaystyle \mathrm{\Phi }_{n_1}^{}(𝐫_e,𝐫_h)(\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_e}\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_h})\mathrm{\Phi }_{n_2}(𝐫_e,𝐫_h)\mathrm{d}^3𝐫_e\mathrm{d}^3𝐫_h},`$
$`F_a(n_1,n_2,𝐤)=\left({\displaystyle \frac{\mathrm{}k}{2Mc_a}}\right)^{1/2}{\displaystyle \mathrm{\Phi }_{n_1}^{}(𝐫_e,𝐫_h)(\sigma _e\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_e}\sigma _h\mathrm{e}^{\mathrm{i}\mathrm{𝐤𝐫}_h})\mathrm{\Phi }_{n_2}(𝐫_e,𝐫_h)\mathrm{d}^3𝐫_e\mathrm{d}^3𝐫_h}.`$ (5)
The linear response of the exciton to the electromagnetic field is described by using the retarded Green function of the electric current operators

$`𝐣(t){\displaystyle \underset{n}{}}𝐝_n[a_n(t)+a_n^{}(t)],`$ (6)
here $`𝐝_n`$ denotes an effective dipole moment of the exciton (Elliott 1957, Mahan 2000). The spectral density of the linear response function is determined by the causal one–particle functions $`G_{nn^{^{}}}(t)=\mathrm{i}T\{a_n(t)a_n^{^{}}^{}\}`$ (where the average is taken with Hamiltonian (4)) which we evaluate solving the Dyson equation. We calculate the spectral function $`A(\omega )2\mathrm{I}\mathrm{m}G_{00}^r(\omega )=2\mathrm{I}\mathrm{m}G_{00}(\omega +\mathrm{i0}^+)`$ and its time course $`A(t)=(2\pi )^1_{\mathrm{}}^{\mathrm{}}A(\omega )\mathrm{e}^{\mathrm{i}\omega t}d\omega `$. In order to determine the one–particle causal function, we evaluate the components of the mass operator using standard method of the solution of the Green function equations of motion

$`\left(\mathrm{i}\mathrm{}{\displaystyle \frac{\mathrm{d}}{\mathrm{d}t}}E_n\right)G_{nn^{^{}}}(t){\displaystyle \frac{1}{N^{1/2}}}{\displaystyle \underset{n_1,𝐤s}{}}F_s(n,n_1,𝐤)R_{n_1n^{^{}}}(𝐤s,t)=\delta (t)\delta _{nn^{^{}}},`$ (7)
where

$$R_{n_1n^{^{}}}(𝐤s,t)=\frac{\mathrm{i}}{\mathrm{}}T\{a_{n_1}(t)[b_{𝐤s}(t)+b_{𝐤s}^{}(t)]a_n^{^{}}^{}(0)\},$$
(8)
with additional condition $`\stackrel{~}{\phi }_{𝐤s}(t)b_{𝐤s}(t)+b_{𝐤s}^{}(t)=0`$ (Martin 1959, Engelsberg 1963). Its Fourier transform takes the form of the Dyson equation

$$G_{nn^{^{}}}(\omega )=G_{nn_1}^{(0)}(\omega )+\underset{n_1n_2}{}G_{nn_1}^{(0)}(\omega )\mathrm{\Sigma }_{n_1n_2}(\omega )G_{n_2n^{^{}}}(\omega ).$$
(9)
Neglecting the off diagonal Green functions, one finds the diagonal elements of the mass operator

$`\mathrm{\Sigma }_{nn}(\omega )={\displaystyle \frac{1}{N}}{\displaystyle \underset{𝐤s}{}}{\displaystyle \underset{n_1}{}}F_s(n,n_1,𝐤)F_s(n_1,n,𝐤)\{{\displaystyle \frac{\mathrm{\Gamma }_{n_1n,𝐤s}(\omega \omega _{𝐤s},\omega _{𝐤s})[1+n(\mathrm{}\omega _{𝐤s})]}{\mathrm{}(\omega \omega _{𝐤s})E_{n_1}\mathrm{\Sigma }_{n_1n_1}(\omega \omega _{𝐤s})}}`$
$`+{\displaystyle \frac{\mathrm{\Gamma }_{n_1n,𝐤s}(\omega +\omega _{𝐤s},\omega _{𝐤s})n(\mathrm{}\omega _{𝐤s})}{\mathrm{}(\omega +\omega _{𝐤s})E_{n_1}\mathrm{\Sigma }_{n_1n_1}(\omega +\omega _{𝐤s})}}\}.`$ (10)
Here $`n(x)=(\mathrm{e}^{x/T}1)^1`$, and $`\mathrm{\Gamma }_{nn^{^{}},𝐤s}(\omega _1,\omega _2)`$ denotes the Fourier transform of a vertex function

$`\mathrm{\Gamma }_{nn^{^{}},𝐤s}(t,t^{^{}}){\displaystyle \frac{\delta G_{nn^{^{}}}^1(t)}{F_s(n,n^{^{}},𝐤)\delta \stackrel{~}{\phi }_{𝐤s}(t^{^{}})}}.`$ (11)
satisfying $`\mathrm{\Gamma }_{nn,𝐤s}(\omega ,\omega _1)1\mathrm{}^1\mathrm{d}\mathrm{\Sigma }_{nn}/\mathrm{d}\omega `$ when consider terms of the lowest order in $`𝐤`$. Let us denote real end imaginary part of the mass operator, respectively, $`\mathrm{Re}\mathrm{\Sigma }_{00}(\omega )\mathrm{\Delta }(\omega )`$, $`\mathrm{Im}\mathrm{\Sigma }_{00}(\omega )\gamma (\omega )`$.

We may solve the mass operator equation (10) with the assumption that the dressed exciton is a durable composite particle which is undamped (Suna 1964). It corresponds to the strictly solvable one level model of (Krummheuer 2002). We expect in this case that the exciton Green function has a real pole at frequency corresponding to the exciton–polaron energy. In the frequency region in vicinity of this pole, the imaginary part of the mass operator can be neglected compared to the real part, which allows us to write the self–consistent equation for $`\mathrm{\Delta }(\omega )`$ (assuming $`\mathrm{\Delta }(\omega )\mathrm{\Delta }=\mathrm{const}`$)

$`\mathrm{\Delta }{\displaystyle \frac{\mathrm{}}{N}}{\displaystyle \underset{𝐤}{}}J_{00}^o(𝐤)\left\{{\displaystyle \frac{[1+n(\mathrm{}\omega _{𝐤o})]}{E_0\stackrel{~}{E}_n\mathrm{}\omega _{𝐤o}}}+{\displaystyle \frac{n(\mathrm{}\omega _{𝐤o})}{E_0\stackrel{~}{E}_n+\mathrm{}\omega _{𝐤o}}}\right\}`$ (12)
which may be solved exactly ($`\stackrel{~}{E}_n=E_0\mathrm{\Delta }`$, $`J_{nn^{^{}}}^s(𝐤)=F_s(n,n^{^{}},𝐤)F_s(n^{^{}},n,𝐤)`$). The energy shift due to the interaction with LA phonons is negligible. One can calculate the form factors

$`J_{00}^o(𝐤)={\displaystyle \frac{\pi e^2\mathrm{}\mathrm{\Omega }}{18\upsilon \stackrel{~}{ϵ}}}(L_e^2L_h^2)^2\mathrm{e}^{l_{}k_{}^2/2l_zk_z^2/2},`$
$`J_{00}^a(𝐤)={\displaystyle \frac{\mathrm{}k}{2Mc_a}}(\sigma _e\sigma _h)^2\mathrm{e}^{l_{}k_{}^2/2l_zk_z^2/2},`$ (13)
(here $`l=l_el_h`$, $`l_z=l_{ze}l_{zh}`$, $`L_e=\sqrt{\frac{\mathrm{}}{m_e^{}\omega _m}}`$, $`L_h=\sqrt{\frac{\mathrm{}}{m_h^{}\omega _m}}`$, and $`\omega _m=\sqrt{\frac{m_e^{}}{m}(\omega _0^e)^2+\frac{m_h^{}}{m}(\omega _0^h)^2}`$, $`m=m_e^{}+m_h^{}`$) (Davydov 1976).

However, we intend to describe the dressed exciton as a damped quasiparticle at non zero temperature range. When include many exciton energy levels, the damping is a consequence of the inclusion of phonon dispersion which is responsible for the interaction between the dressed exciton and the phonon subsystem (Davydov 1972). We solve (10) in two iteration steps in the vicinity of $`\mathrm{}\omega =E_0`$, taking in the first approximation the vertex functions $`\mathrm{\Gamma }_{n_1n^{^{}},𝐤s}(\omega ,\omega _1)=1`$, as done in (Moskalenko 1968). Starting from $`\mathrm{\Delta }_{(0)}(\omega )=0`$, $`\gamma _{(0)}(\omega )=0^+`$ and assuming that $`\mathrm{\Delta }(\omega )\mathrm{const}`$, we find in the first iteration step

$`\mathrm{\Delta }_{(1)}(\omega )\mathrm{\Delta }_{(1)}(E_0/\mathrm{})=\mathrm{\Delta }^{^{}}={\displaystyle \frac{\mathrm{}}{N}}{\displaystyle \underset{𝐤}{}}{\displaystyle \frac{b_nJ_{0n}^o(𝐤)}{E_0E_n\mathrm{}\omega _{𝐤o}}},`$
$`\gamma _{(1)}(\omega )={\displaystyle \frac{\mathrm{}\pi }{N}}{\displaystyle \underset{𝐤}{}}J_{00}^a(𝐤)\left\{[1+n(\mathrm{}\omega _{𝐤a})]\delta (\mathrm{}\omega E_0\mathrm{}\omega _{𝐤a})+n(\mathrm{}\omega _{𝐤a})\delta (\mathrm{}\omega E_0+\mathrm{}\omega _{𝐤a})\right\}.`$ (14)
Here $`b_n`$ denotes the $`n`$–th level degeneracy rank ($`b_n=1,2`$). The optical phonon contribution to $`\gamma (\omega )`$, is significant for $`\mathrm{}\omega E_n\pm \mathrm{}\mathrm{\Omega }`$ only. We include the LO phonon influence on $`\gamma (\omega )`$, introducing an effective constant to $`J_{00}^a(𝐤)`$, which does not influence the time of fast dressing with phonons but it determines the relaxation time at non zero $`T`$. This constant will be estimated from the sum rule $`|A(t=0)|=1`$ for $`T=0`$. In the second step, the relation $`\mathrm{\Delta }_{(1)}(\omega )\gamma _{(1)}(\omega )`$ enables one to neglect the $`\gamma _{(1)}(\omega )`$ in the denominators of (10). It leads to

$`\mathrm{\Delta }_{(2)}(\omega )\mathrm{\Delta }_{(2)}(E_0/\mathrm{})=\mathrm{\Delta }^{^{\prime \prime }}\mathrm{\Delta }_{(2)}(\stackrel{~}{E}_0/\mathrm{})+\mathrm{}^1{\displaystyle \frac{\mathrm{d}\mathrm{\Delta }_{(2)}}{\mathrm{d}\omega }}|_{\omega =\stackrel{~}{E}_0/\mathrm{}}\mathrm{\Delta }^{^{}}=\mathrm{\Delta }^{^{}}Z^1,`$
$`\gamma _{(2)}(\omega )=\gamma _{(1)}(\omega +\mathrm{\Delta }^{^{}}/\mathrm{}),`$ (15)
where $`\stackrel{~}{E}_n=E_n\mathrm{\Delta }^{^{}}`$, $`\mathrm{\Delta }_{(2)}(\stackrel{~}{E}_0/\mathrm{})=\frac{\mathrm{}}{N}_𝐤\frac{b_nJ_{0n}^o(𝐤)}{\stackrel{~}{E}_0\stackrel{~}{E}_n\mathrm{}\omega _{𝐤o}}=\mathrm{\Delta }^{^{}}`$. Continuing the iteration process we would arrive to a self consistent equation for $`\mathrm{\Delta }`$ similar to (12), however, after infinite number of the approximations. We find

$`\gamma _{(2)}(x)=Z^1\alpha x^3\mathrm{e}^{\beta x^2}f(x)\left\{n(x)\theta (x)+\left[1+n(x)\right]\theta (x)\right\}`$ (16)
where $`x=\mathrm{}\omega E_0+\mathrm{\Delta }^{^{}}`$, $`f(x)=_{n=0}^{\mathrm{}}\frac{\left[\beta x^2(l_z^2/l_{}^21)\right]^n}{(2n+1)n!}`$, $`Z`$ denotes the vertex function renormalisation factor ($`Z=|1\mathrm{}^1\mathrm{d}\mathrm{\Delta }/\mathrm{d}\omega |^1`$). We write the spectral function in the form

$`A(\omega )=Z{\displaystyle \frac{\mathrm{}2\tau ^1(\omega )}{[\mathrm{}\omega E_0+Z^1\mathrm{\Delta }^{^{}}]^2+\tau ^2(\omega )}},`$ (17)
where $`\tau ^1(\omega )=Z\gamma (\omega )`$ (Langreth 1964, Mahan 1966). Since at zero temperature, the renormalisation factor may be calculated directly

$$Z1+\frac{\mathrm{}}{N}\underset{𝐤}{}\frac{b_nJ_{0n}^o(𝐤)}{(E_0E_n\mathrm{}\omega _{𝐤o})^2},$$
(18)
the sum rule $`|A(t=0)|=1`$ enables us to estimate the effective damping constant $`\alpha `$. At higher temperatures, when the phonon dispersion effects are strong we evaluate $`Z`$ using the same condition ($`|A(t=0)|=1`$).

## 3 Results and conclusions

We have evaluated the interaction form factors $`J_{nn^{^{}}}^s(𝐤)`$ taking the function of the non–interacting electron and hole system as the first approximation for the exciton wave function $`\mathrm{\Phi }_n(𝐫_e,𝐫_h)=\mathrm{\Psi }_{n_em_e}^{(e)}(𝐫_e)\mathrm{\Psi }_{00}^{(h)}(𝐫_e)`$, where

$`\mathrm{\Psi }_{nm}^{(i)}(𝐫)=\psi _{nm}^{(i)}(r_{},\phi )\varphi ^{(i)}(z)={\displaystyle \frac{N_{nm}^{(i)}}{(2\pi )^{1/2}}}\left({\displaystyle \frac{r_{}^2}{l_i^2}}\right)^{|m|/2}\mathrm{e}^{\frac{r_{}^2}{2l_i^2}}L_n^{|m|}\left({\displaystyle \frac{r_{}^2}{l_i^2}}\right)\mathrm{e}^{\mathrm{i}m\phi }{\displaystyle \frac{1}{\pi ^{1/2}l_{iz}}}\mathrm{e}^{\frac{z^2}{2l_{iz}^2}},`$
$`N_{nm}^{(i)}={\displaystyle \frac{1}{\pi ^{1/2}l_i}}\left({\displaystyle \frac{n!}{(n+|m|)!}}\right).`$ (19)
Since $`\omega _0^i\omega _z^i`$, we consider only the first level for the quantisation in z–axis direction. A fact that an effective mass of a hole is large in comparison to the electron effective mass, enables one to neglect the hole levels different than the lowest one (of $`n_h=0`$, $`m_h=0`$). Defining the functions

$`I_{n^{^{}}n^{^{\prime \prime }}}^{(i)}(𝐤)={\displaystyle _0^{\mathrm{}}}{\displaystyle _0^{2\pi }}\psi _{n^{^{\prime \prime }}}^{(i)}(r_{},\phi )\mathrm{e}^{\mathrm{i}k_{}r_{}\mathrm{cos}(\phi )}\psi _n^{^{}}^{(i)}(r_{},\phi )dr_{}d\phi `$
$`\times {\displaystyle _{\mathrm{}}^{\mathrm{}}}\varphi ^{(i)}(z)\mathrm{e}^{\mathrm{i}k_zz}\varphi ^{(i)}(z)\mathrm{d}z=I_{n^{^{}}n^{^{\prime \prime }}}^{(i)}(k_{})\mathrm{e}^{2(k_zl_{iz}/2)^2},`$ (20)
where the index $`n`$ replaces both $`n_e`$,$`m_e`$ quantum numbers, we write the form factors in the form

$`J_{nn^{^{}}}^o(𝐤)={\displaystyle \frac{2\pi e^2\mathrm{}\mathrm{\Omega }}{\upsilon \stackrel{~}{ϵ}k^2}}[I_{nn^{^{}}}^{(e)}(𝐤)I_{nn^{^{}}}^{(h)}(𝐤)]^2,`$
$`J_{nn^{^{}}}^a(𝐤)={\displaystyle \frac{\mathrm{}k}{2Mc_a}}[\sigma _eI_{nn^{^{}}}^{(e)}(𝐤)\sigma _hI_{nn^{^{}}}^{(h)}(𝐤)]^2.`$ (21)
We perform the calculations of the energy shift including ten lowest exciton energy levels, for the two confinement sizes $`l_e=6`$nm$`l_h`$ and $`l_e=3`$nm$`l_h`$. The following material parameters suitable to the InAs/GaAs QD have been used $`m_e^{}=0.067m_0`$, $`m_h^{}=0.38m_0`$, $`ϵ_0=12.9`$, $`ϵ_{\mathrm{}}=10.9`$, $`\mathrm{}\mathrm{\Omega }=36.4`$meV, $`c_a=4.810^3`$m/s. The integral form factors of the exciton–LO phonon interaction $`J_{0n}^o=(\mathrm{}/N)_𝐤J_{0n}^o(𝐤)`$ multiplied by the level degeneracy rank corresponding to the exciton energies $`E_n`$ are presented in the table.

The inclusion of many exciton levels influences the dressed exciton energy shift. It is responsible for its substantial increase (from 0.5meV found in one level approximation to 3.6meV when include ten levels for $`l_e=3`$nm, and from 0.35meV to 2.9meV for $`l_e=6`$nm). The other material constants $`\sigma _e=6.7`$eV, $`\sigma _e=2.7`$eV, $`\rho =5.36`$g/cm3 (Adachi 1985) are useful for estimations.

The spectral density and its inverse Fourier transform calculated including many exciton levels and including realistic asymmetry of the QD ($`l_{ze}/l_e=1/3`$) are plotted in Figs 1,2. Generally, the LA channel of dressing gives for the typical QDs the picosecond scale of dressing. Inclusion of the LO channel does not modify significantly the overall LO and LA dressing kinetics in comparison to LA channel solely (Takagahara 1999). Thus the LA channel of dressing gives the limit for adiabatic creation of exciton–polaron in InAs/GaAs QD. The slope of the time courses of spectral functions is related to damping of the dressed exciton at non zero temperature. The relaxation time is strongly influenced by the size of QD.

Let us emphasise that our results for time dependence of the response functions (Fig. 1,2) coincide with the experimental results by Borri (2001).

The work was supported by E.C.Project IST-1999-11311 (SQID) and by KBN Project PB 2 PO3B 055 18.

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Figure captions:
Fig. 1. Time course of the response function and spectral intensity for $`l_e=3`$nm, $`l_z/l_e=1/3`$
Fig. 2. Time course of the response function and spectral intensity for $`l_e=6`$nm, $`l_z/l_e=1/3`$

Table caption:
Exciton energy levels $`E_n`$ and corresponding integral form factors $`J_{0n}^o`$ multiplied by n-th level degeneracy rank $`b_n`$.

| $`l_e=3`$nm | | $`l_e=6`$nm | |
| --- | --- | --- | --- |
| $`E_n`$\[meV\] | $`b_nJ_{0n}^o`$\[meV2\] | $`E_n`$\[meV\] | $`b_nJ_{0n}^o`$\[meV2\] |
| 88.9 | 13.1 | 7.87 | 12.5 |
| 113.3 | 2$``$ 39.0 | 15.7 | 2$``$18.8 |
| 134.0 | 36.0 | 23.3 | 21.5 |
| 135.8 | 2$``$ 16.9 | 23.8 | 2$``$9.9 |
| 152.0 | 2$``$ 18.4 | 29.6 | 2$``$10.4 |
| 155.6 | 2$``$ 5.6 | 30.8 | 2$``$3.5 |
| 167.9 | 18.2 | 34.8 | 7.4 |
| 169.4 | 2$``$ 10.7 | 35.5 | 2$``$4.7 |
| 183.8 | 2$``$ 13.0 | 39.5 | 2$``$5.4 |
| 199.0 | 11.5 | 44.2 | 4.0 |