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# On intervals in some posets of forests

## 0 Introduction

The aim of this article is to study the poset $`\mathrm{For}(I)`$ attached to a finite set $`I`$ which was introduced in  in relation with a Hopf operad of forests of binary trees. The underlying set of $`\mathrm{For}(I)`$ is the set of leaf-labeled forests of rooted binary trees with label set $`I`$. The main result is the following theorem.

###### Theorem 0.1

The characteristic polynomial of any interval in the poset $`\mathrm{For}(I)`$ has only nonnegative integer roots.

Furthermore, an explicit description of the roots is obtained for all intervals. In particular, this gives simple product expressions for all Möbius numbers.

The simplest case is the interval between the minimal element $`E`$ of the poset $`\mathrm{For}(I)`$ and a rooted binary leaf-labeled tree $`T`$ on $`I`$. To each inner vertex of $`T`$, one associates the product of the number of leaves of its two subtrees. These positive integers are the roots of the characteristic polynomial of $`[E,T]`$. Figure 1 displays two examples of this computation.

When the tree $`T`$ is a comb, the interval $`[E,T]`$ is isomorphic to the partition lattice and the roots are $`1,2,\mathrm{},n`$, where $`n+1`$ is the cardinal of $`I`$, see the right example in Figure 1. One recovers the well-known factorization of the characteristic polynomial of the partition lattice, by a method which differs from those reviewed in .

The other main result is an explanation of the coincidence of some characteristic polynomials observed from the obtained description. This is shown to be a consequence of some isomorphisms between the intervals.

The strategy of proof is to decompose as much as possible the intervals as products of simpler intervals. This gives a reduction to the case of some special intervals, for which another kind of decomposition can be done.

The first section is devoted to general results on these posets and to the relation between combs and the partition lattice. The intervals and their decompositions are studied in the second section. The third section contains the proof that these posets are ranked by the number of inner vertices. In the fourth section, invariants of the intervals are computed, including the characteristic polynomials. The last section contains the proof of some expected isomorphisms between the intervals.

## 1 Definition of posets

### 1.1 Notations

A tree is a leaf-labeled rooted binary tree and a forest is a set of such trees. Vertices are either inner vertices (valence $`3`$) or leaves and roots (valence $`1`$). By convention, edges are oriented towards the root. Leaves are bijectively labeled by a finite set. Trees and forests are pictured with their roots down and their leaves up, but are not to be considered as planar. A leaf is an ancestor of a vertex if there is a path from the leaf to the root going through the vertex.

If $`T_1`$ and $`T_2`$ are trees on $`I_1`$ and $`I_2`$, let $`T_1T_2`$ be the tree on $`I_1I_2`$ obtained by grafting the roots of $`T_1`$ and $`T_2`$ on a new inner vertex. If $`F_1,F_2,\mathrm{},F_k`$ are forests on $`I_1,I_2,\mathrm{},I_k`$, let $`F_1F_2\mathrm{}F_k`$ be their disjoint union. If $`F`$ is the disjoint union of a forest on $`J`$ and a forest on $`J^{}`$, these restricted forests are denoted by $`F[J]`$ and $`F[J^{}]`$. For a forest $`F`$, let $`V(F)`$ be the set of its inner vertices. The number of trees in a forest $`F`$ on $`I`$ is the difference between the cardinal of $`I`$ and the cardinal of $`V(F)`$.

### 1.2 Posets of forests

Let $`F`$ and $`F^{}`$ be forests on the label set $`I`$. Then set $`FF^{}`$ if there is a topological map from $`F`$ to $`F^{}`$ with the following properties:

1. It is increasing with respect to orientation towards the root.
2. It maps inner vertices to inner vertices injectively.
3. It restricts to the identity of $`I`$ on leaves.
4. Its restriction to each tree of $`F`$ is injective.

In fact, such a topological map from $`F`$ to $`F^{}`$ is determined up to isotopy by the images of the inner vertices of $`F`$. One can recover the map by joining the image of an inner vertex of $`F`$ in $`F^{}`$ with the leaves of $`F^{}`$ which were its ancestor leaves in $`F`$.

Remark that there can be different $`F`$ lower than a given $`F^{}`$ with the same image of $`V(F)`$ in $`V(F^{})`$.

###### Lemma 1.1

Let $`F,F^{}`$ be two distinct forests on $`I`$. If $`FF^{}`$ then the cardinal of $`V(F)`$ is strictly less than the cardinal of $`V(F^{})`$.

* Proof. Assume that $`FF^{}`$ and the cardinal of $`V(F)`$ is equal to that of $`V(F^{})`$. Then $`F`$ and $`F^{}`$ have the same number of trees. But each tree of $`F`$ is contained in a tree of $`F^{}`$ by connectivity. Each tree of $`F^{}`$ contains at least one tree of $`F`$ by injectivity on vertices. Therefore each tree of $`F`$ is contained in exactly one tree of $`F^{}`$. As these two trees have the same number of vertices, they must be equal. Hence $`F=F^{}`$.

###### Proposition 1.2

The relation $``$ defines a partial order on the set $`\mathrm{For}(I)`$ of forests on $`I`$.

* Proof. Reflexivity is given by the identity map. Transitivity is easy to check for each of the four required properties. Antisymmetry is clear by Lemma 1.1.

A counterexample, not injective on inner vertices, is given in Figure 2 and an example in Figure 3.

###### Lemma 1.3

If $`T_1`$ and $`T_2`$ are trees on $`I_1`$ and $`I_2`$ then $`T_1T_2T_1T_2`$.

* Proof. Obvious.

Lemma 1.3 implies that, for each forest $`F`$ which is not a tree, there exists a forest $`F^{}`$ with strictly less trees such that $`FF^{}`$. Lemma 1.1 implies that trees are maximal elements. Therefore the maximal elements of the poset $`\mathrm{For}(I)`$ are exactly the trees. The forest without inner vertex is the unique minimal element, denoted by $`E`$.

The intervals in the poset $`\mathrm{For}(I)`$ are not semimodular in general, as can be seen on the interval depicted in Figure 4.

### 1.3 Relation to the partition lattice

A comb is a tree such that each inner vertex has at least one of its two subtrees reduced to an edge.

###### Proposition 1.4

The interval between $`E`$ and a comb $`C`$ on the set $`I`$ is isomorphic to the partition lattice of the set $`I`$.

* Proof. Remark first that a forest which is lower than a comb is necessarily composed of combs. The isomorphism $`\varphi `$ is given by mapping a forest of combs to the partition of $`I`$ defined on the leaves by the combs. Let $`J`$ be a subset of $`I`$. Then there is exactly one comb $`C_J`$ with leaf set $`J`$ such that there exists an injective topological map from $`C_J`$ to $`C`$ which respects orientation and restricts to the identity of $`J`$ on leaves.

This implies that each partition of $`I`$ can in only one way be realized as the leaf set of a forest of combs which is lower than $`C`$. Hence $`\varphi `$ is bijective. That the map $`\varphi `$ is an isomorphism of posets follows easily from the description of the partial order, which is seen to coincide via $`\varphi `$ with the refinement order on partitions.

## 2 Properties of intervals

### 2.1 Decomposition by connected components

Let $`FF^{}`$ be forests on $`I`$. Let $`F^{}=T_1^{},T_2^{},\mathrm{},T_k^{}`$ seen as a set of trees $`T_j^{}`$ on $`I_j`$ with $`I=I_1I_2\mathrm{}I_k`$. Then $`F`$ can be uniquely decomposed as an union of forests $`F_j=F[I_j]`$ on $`I_j`$ satisfying $`F_jT_j^{}`$.

###### Proposition 2.1

The interval $`[F,F^{}]`$ is isomorphic to the product of the intervals $`[F_j,T_j^{}]`$ in $`\mathrm{For}(I_j)`$ for $`1jk`$.

* Proof. Each element of this interval can in the same way be uniquely decomposed as an union of forests on $`I_j`$. The conditions defining the partial order then become equivalent to independent conditions on each part $`I_j`$.

One can therefore restrict the attention to intervals between a forest and a tree.

### 2.2 Elements lower than a tree

Let $`T`$ be a tree on the set $`I`$. Let us describe all elements $`F`$ of $`\mathrm{For}(I)`$ which are lower than $`T`$. The binary tree $`T`$ defines a partition $`I=I_1I_2`$ and two subtrees $`T_1`$ on $`I_1`$ and $`T_2`$ on $`I_2`$.

If $`F_1T_1`$ and $`F_2T_2`$ then clearly $`F_1F_2T`$.

Let $`F_1,F_2`$ be forests with $`F_1T_1`$ and $`F_2T_2`$. Let $`J_1`$ (resp. $`J_2)`$ be a chosen part of $`I_1`$ (resp. $`I_2`$) corresponding to a chosen tree of $`F_1`$ (resp. $`F_2`$). Denote by $`G(F_1,J_1,F_2,J_2)`$ the forest constructed from the disjoint union of $`F_1`$ and $`F_2`$ by grafting a new inner vertex to the roots of the chosen trees. This forest satisfies $`G(F_1,J_1,F_2,J_2)T`$.

###### Proposition 2.2

A forest $`F`$ lower than $`T`$ is either the disjoint union $`F_1F_2`$ where $`F_1T_1`$ and $`F_2T_2`$ or is equal to $`G(F_1,J_1,F_2,J_2)`$ where $`F_1T_1`$, $`F_2T_2`$ and $`J_1`$, $`J_2`$ are parts of $`I_1`$,$`I_2`$ corresponding to trees of $`F_1`$,$`F_2`$.

* Proof. Two forests $`F_1`$ and $`F_2`$ can be defined as follows. Consider the inner vertices of $`F`$ having only elements of $`I_1`$ as ancestors. By joining them in $`T`$ to their ancestor leaves, one gets $`F_1`$ on $`I_1`$ which satisfies $`F_1T_1`$. The same construction gives $`F_2`$ on $`I_2`$ with $`F_2T_2`$.

Assume first that the image of $`V(F)`$ in $`V(T)`$ does not contain the lowest inner vertex of $`T`$. From the definition of the poset, $`F`$ is in fact lower than $`T_1T_2`$ and is the disjoint union $`F_1F_2`$.

Assume now on the contrary that the image of $`V(F)`$ in $`V(T)`$ contains the lowest inner vertex of $`T`$. By injectivity on inner vertices, there exists a unique tree $`T^{}`$ of $`F`$ which has an inner vertex mapped to the lower inner vertex of $`T`$. By injectivity on trees, the tree $`T^{}`$ can be written $`T_1^{}T_2^{}`$ where $`T_1^{}`$ (resp. $`T_2^{}`$) has leaf set $`J_1I_1`$ (resp. $`J_2I_2`$). The tree $`T_1^{}`$ (resp. $`T_2^{}`$) is a tree of $`F_1`$ (resp. $`F_2`$) and $`F`$ is indeed equal to $`G(F_1,J_1,F_2,J_2)`$.

### 2.3 Intervals under a tree

Let $`T`$ be a tree and $`F`$ a forest on the set $`I`$ such that $`FT`$ and the image of $`V(F)`$ in $`V(T)`$ contains the lowest inner vertex of $`T`$. This implies that $`F`$ can be written $`G(F_1,J_1,F_2,J_2)`$ as explained in the previous section.

###### Proposition 2.3

The interval $`[F,T]`$ is isomorphic to the product of the intervals $`[F_1,T_1]`$ in $`\mathrm{For}(I_1)`$ and $`[F_2,T_2]`$ in $`\mathrm{For}(I_2)`$.

* Proof. Let $`F^{}`$ be an element of the interval $`[F,T]`$. Necessarily the image of $`V(F^{})`$ contains the lowest vertex of $`T`$. Therefore one can write $`F^{}=G(F_1^{},J_1^{},F_2^{},J_2^{})`$ with $`F_1^{}T_1`$ and $`F_2^{}T_2`$. By definition of the partial order, the inequality $`FF^{}`$ implies that $`F_1F_1^{}`$, $`F_2F_2^{}`$ and that $`J_1^{}`$ (resp. $`J_2^{}`$) must contain $`J_1`$ (resp. $`J_2`$). It follows that $`J_1^{}`$ and $`J_2^{}`$ are uniquely determined for a given $`F_1^{}`$ and $`F_2^{}`$. Therefore, any pair $`(F_1^{},F_2^{})`$ with $`F_1F_1^{}T_1`$ and $`F_2F_2^{}T_2`$ can be uniquely extended to an element of $`[F,T]`$.

The elements of the interval $`[F,T]`$ are therefore in bijection with pairs $`(F_1^{},F_2^{})`$ in $`[F_1,T_1]\times [F_2,T_2]`$.

The conditions defining the partial order do not depend on $`J_1`$ and $`J_2`$, and are mapped by the bijection to independent conditions on $`I_1`$ and $`I_2`$. Hence the bijection is an isomorphism of posets.

### 2.4 Special intervals

Let $`F`$ be a forest and $`T`$ be a tree on the set $`I`$ with $`FT`$. Assume that the image of $`V(F)`$ in $`V(T)`$ does not contain the lowest inner vertex of $`T`$, that is to say $`F`$ is a disjoint union $`F_1F_2`$ on $`I_1`$ and $`I_2`$. The intervals of the form $`[F,T]`$ for such $`F`$ and $`T`$ are called special intervals.

###### Proposition 2.4

There are three kinds of sub-intervals in a special interval $`[F,T]`$:

1. $`[F_1^{}F_2^{},F_1^{\prime \prime }F_2^{\prime \prime }]`$ with $`F_1F_1^{}F_1^{\prime \prime }T_1`$ and $`F_2F_2^{}F_2^{\prime \prime }T_2`$. This interval is isomorphic to $`[F_1^{},F_1^{\prime \prime }]\times [F_2^{},F_2^{\prime \prime }]`$.
2. $`[G(F_1^{},J_1^{},F_2^{},J_2^{}),G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })]`$ with $`F_1F_1^{}F_1^{\prime \prime }T_1`$ and $`F_2F_2^{}F_2^{\prime \prime }T_2`$ where $`J_1^{\prime \prime }`$ and $`J_2^{\prime \prime }`$ are the unique parts of $`F_1^{\prime \prime }`$ and $`F_2^{\prime \prime }`$ containing $`J_1^{}`$ and $`J_2^{}`$. This interval is isomorphic to $`[F_1^{},F_1^{\prime \prime }]\times [F_2^{},F_2^{\prime \prime }]`$.
3. $`[F_1^{}F_2^{},G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })]`$ with $`F_1F_1^{}F_1^{\prime \prime }T_1`$, $`F_2F_2^{}F_2^{\prime \prime }T_2`$, and $`J_1^{\prime \prime },J_2^{\prime \prime }`$ are arbitrary parts of $`F_1^{\prime \prime }`$ and $`F_2^{\prime \prime }`$.

* Proof. First, let us determine which elements $`F^{}`$ can be lower than $`T`$ and greater than $`F`$. If $`F^{}`$ is a disjoint union $`F_1^{}F_2^{}`$, then it is necessary and sufficient that $`F_1F_1^{}T_1`$ and $`F_2F_2^{}T_2`$. If $`F^{}=G(F_1^{},J_1^{},F_2^{},J_2^{})`$, then necessary and sufficient conditions are also that $`F_1F_1^{}T_1`$ and $`F_2F_2^{}T_2`$.

Let us discuss now the possible intervals according to the type of their bounds. First, it is not possible to have a relation $`G(F_1^{},J_1^{},F_2^{},J_2^{})(F_1^{\prime \prime }F_2^{\prime \prime })`$, because the lowest inner vertex is present in the first element and not in the second one, which would contradict injectivity.

Let us study each of the three remaining cases.

Case $`[,]`$: One can apply Prop. 2.1. The interval $`[F_1^{}F_2^{},F_1^{\prime \prime }F_2^{\prime \prime }]`$ is non-empty if and only if $`F_1^{}F_1^{\prime \prime }`$ and $`F_2^{}F_2^{\prime \prime }`$. If these conditions are fulfilled, this interval is isomorphic to the claimed product.

Case $`[G,G]`$: the interval $`[G(F_1^{},J_1^{},F_2^{},J_2^{}),G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })]`$. Let $`F_1^{\prime \prime }=f_1^{\prime \prime }T_1^{\prime \prime }`$ where $`T_1^{\prime \prime }=F_1^{\prime \prime }[J_1^{\prime \prime }]`$ is a tree and similarly let $`F_2^{\prime \prime }=f_2^{\prime \prime }T_2^{\prime \prime }`$ where $`T_2^{\prime \prime }=F_2^{\prime \prime }[J_2^{\prime \prime }]`$ is a tree. Then $`G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })`$ is equal to $`f_1^{\prime \prime }f_2^{\prime \prime }(T_1^{\prime \prime }T_2^{\prime \prime })`$. One can then decompose the interval as a product by Prop. 2.1. By applying Prop. 2.2 to the interval under $`T_1^{\prime \prime }T_2^{\prime \prime }`$, the product interval is non-empty if and only if one has $`F_1^{}F_1^{\prime \prime }`$ and $`F_2^{}F_2^{\prime \prime }`$ and the parts $`J_1^{\prime \prime }`$ and $`J_2^{\prime \prime }`$ contains respectively the parts $`J_1^{}`$ and $`J_2^{}`$. When these conditions are satisfied, Prop. 2.3 shows that this interval is isomorphic to the claimed product.

Case $`[,G]`$: the interval $`[F_1^{}F_2^{},G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })]`$. Let $`F_1^{\prime \prime }=f_1^{\prime \prime }T_1^{\prime \prime }`$ where $`T_1^{\prime \prime }=F_1^{\prime \prime }[J_1^{\prime \prime }]`$ is a tree and similarly let $`F_2^{\prime \prime }=f_2^{\prime \prime }T_2^{\prime \prime }`$ where $`T_2^{\prime \prime }=F_2^{\prime \prime }[J_2^{\prime \prime }]`$ is a tree. Then $`G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })`$ is equal to $`f_1^{\prime \prime }f_2^{\prime \prime }(T_1^{\prime \prime }T_2^{\prime \prime })`$. One can then decompose the interval as a product by Prop. 2.1. By applying Prop. 2.2 to the interval under $`T_1^{\prime \prime }T_2^{\prime \prime }`$, the product interval is non-empty if and only if one has $`F_1^{}F_1^{\prime \prime }`$ and $`F_2^{}F_2^{\prime \prime }`$.

## 3 Rank property

Say that a finite poset is ranked if it has a unique minimal element $`\widehat{0}`$ and all maximal chains have the same length. Note that this definition differs slightly from the usual definition which requires the uniqueness of the maximal element.

###### Proposition 3.1

The poset $`\mathrm{For}(I)`$ is ranked by the number of inner vertices.

* Proof. The proof is by recursion on the cardinal of $`I`$. The proposition is true by inspection for small $`I`$.

Fix a maximal interval $`[E,T]`$ where $`T`$ is a tree on $`I`$ and $`E`$ is the forest without inner vertices. Consider a maximal chain $`E=F_0\mathrm{}F=F_{k1}F_k=T`$ in $`[E,T]`$. It is clear from Lemma 1.1 that the length $`k`$ is at most the number of inner vertices of $`T`$.

Let us discuss according to the properties of $`F`$.

Assume first that $`F`$ contains the lowest inner vertex of $`T`$. By maximality, there should be no element between $`F`$ and $`T`$, and one can conclude by recursion hypothesis and Prop. 2.3 that either $`F_1=T_1`$ and $`F_2`$ has just one vertex less than $`T_2`$ or the similar situation obtained by exchanging $`1`$ and $`2`$ holds.

Assume on the contrary that $`F`$ does not contain the lowest inner vertex of $`T`$. By maximality, there should be no element between $`F`$ and $`T`$, and one can conclude by recursion hypothesis and Prop. 2.4 that $`F_1=T_1`$ and $`F_2=T_2`$.

Therefore, in both cases, the number of inner vertices of $`F`$ is the number of inner vertices of $`T`$ minus one.

By recursion and Prop. 2.1, the length of all maximal chains of $`[E,F]`$ is the number of inner vertices of $`F`$.

This implies that the length of all maximal chains of $`[E,T]`$ is the number of inner vertices of $`T`$. All trees on $`I`$ have the same number of inner vertices. The proposition is proved.

Note that the corank function in $`\mathrm{For}(I)`$ is given by the number of trees minus one.

## 4 Invariants of intervals

For a standard reference on posets, see .

### 4.1 $`M`$-polynomials and $`Z`$-polynomials

Let $`P`$ be a ranked poset with unique minimal element $`\widehat{0}`$ and unique maximal element $`\widehat{1}`$. Let $`\mathrm{crk}`$ be the corank function on $`P`$, which is defined by $`\mathrm{crk}(a)=\mathrm{rk}(\widehat{1})\mathrm{rk}(a)`$. The degree of the poset is $`\mathrm{deg}(P)=\mathrm{crk}(\widehat{0})`$ .

One defines the $`M`$-polynomial of the poset $`P`$, which is a generating function for the Möbius function, as follows:

$$M(P)=\underset{ab}{}\mu (a,b)x^{\mathrm{crk}(a)}y^{\mathrm{crk}(b)}.$$
(1)
In the same way, one defines the $`Z`$-polynomial, which is a generating function for the zeta function, as follows:

$$Z(P)=\underset{ab}{}x^{\mathrm{crk}(a)}y^{\mathrm{crk}(b)}.$$
(2)
The characteristic polynomial is defined to be

$$\chi (P)=\underset{b}{}\mu (\widehat{0},b)y^{\mathrm{crk}(b)}.$$
(3)
The cardinal polynomial is the generating function for the corank:

$$\mathrm{Card}(P)=\underset{a}{}x^{\mathrm{crk}(a)}.$$
(4)
The Möbius number is $`\mu (P)=\mu (\widehat{0},\widehat{1})`$.

It is clear that the $`M`$-polynomial allows to recover the characteristic polynomial, which in turn contains the Möbius number as leading coefficient. The $`M`$-polynomial also contains the information of the cardinal polynomial.

The cardinal polynomial is also determined by the $`Z`$-polynomial.

The following proposition is classical.

###### Proposition 4.1

Let $`P_1`$ and $`P_2`$ be two such ranked posets and $`P_1\times P_2`$ their product. Then

$$Z_{P_1\times P_2}=Z_{P_1}Z_{P_2}\text{ and }M_{P_1\times P_2}=M_{P_1}M_{P_2}.$$
(5)
###### Lemma 4.2

The value at $`y=1`$ of the $`M`$-polynomial is $`1`$.

* Proof. This is an immediate consequence of the definition of the Möbius function and the existence of $`\widehat{1}`$.

### 4.2 $`Z`$-polynomials of special intervals

Let $`F`$ be a forest and $`T`$ be a tree on the set $`I`$. Assume that $`FT`$ and the image of $`V(F)`$ in $`V(T)`$ does not contain the lowest inner vertex of $`T`$. We keep the notations of section 2.4.

###### Theorem 4.3

The $`Z`$-polynomial of the special interval $`[F,T]`$ (denoted by Z) is determined by the $`Z`$-polynomials of the intervals $`[F_1,T_1]`$ and $`[F_2,T_2]`$ (denoted by $`Z_1`$ and $`Z_2`$). One has

$$Z=xyZ_1Z_2+_x(xZ_1)_x(xZ_2)+x_y(yZ_1)_y(yZ_2).$$
(6)
* Proof. The sum defining $`Z`$ is split in three parts, according to the three different kinds of subintervals in $`[F,T]`$ listed in Prop. 2.4.

The first part is given by

$$\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}x^{1+\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{1+\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })},$$

which is $`xyZ_1Z_2`$.

The second part is given by

$$\begin{array}{c}\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}\underset{J_1^{},J_2^{}}{}x^{\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })}\hfill \\ \hfill =\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}(1+\mathrm{crk}(F_1^{}))(1+\mathrm{crk}(F_2^{}))x^{\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })},\end{array}$$

which is $`_x(xZ_1)_x(xZ_2)`$.

The last part is given by

$$\begin{array}{c}\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}\underset{J_1^{\prime \prime },J_2^{\prime \prime }}{}x^{1+\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })}\hfill \\ \hfill =\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}(1+\mathrm{crk}(F_1^{\prime \prime }))(1+\mathrm{crk}(F_2^{\prime \prime }))x^{1+\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })},\end{array}$$

which is $`x_y(yZ_1)_y(yZ_2)`$.

This concludes the proof of the theorem.

### 4.3 $`M`$-polynomials of special intervals

Let $`F`$ be a forest and $`T`$ be a tree on the set $`I`$. Assume that $`FT`$ and the image of $`V(F)`$ in $`V(T)`$ does not contain the lowest inner vertex of $`T`$. We keep the notations of section 2.4.

###### Theorem 4.4

The $`M`$-polynomial of the special interval $`[F,T]`$ (denoted by $`M`$) depends only on the $`M`$-polynomials of the intervals $`[F_1,T_1]`$ and $`[F_2,T_2]`$ (denoted by $`M_1`$ and $`M_2`$). One has

$$M=xyM_1M_2+(1x)_x(xM_1)_x(xM_2).$$
(7)
* Proof. By recursion on the degree of $`[F,T]`$.

Formula (7) is correct if $`F=T_1T_2`$ and $`T=T_1T_2`$, which is the only possible case of degree $`1`$.

The sum which defines $`M`$ is split in three parts, according to the three different kinds of subintervals in $`[F,T]`$ listed in Prop. 2.4.

The first part is given by

$$\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}\mu (F_1^{},F_1^{\prime \prime })\mu (F_2^{},F_2^{\prime \prime })x^{1+\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{1+\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })},$$

which is $`xyM_1M_2`$.

The second part is given by

$$\begin{array}{c}\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}\underset{\genfrac{}{}{0pt}{}{J_1^{}}{J_2^{}}}{}\mu (F_1^{},F_1^{\prime \prime })\mu (F_2^{},F_2^{\prime \prime })x^{\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })}\hfill \\ \hfill =\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}(1+\mathrm{crk}(F_1^{}))(1+\mathrm{crk}(F_2^{}))\mu (F_1^{},F_1^{\prime \prime })\mu (F_2^{},F_2^{\prime \prime })\\ \hfill x^{\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })},\end{array}$$

which is $`_x(xM_1)_x(xM_2)`$.

The computation of the third part is more complicated. It is given by

$$\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}\left(\underset{\genfrac{}{}{0pt}{}{J_1^{\prime \prime }}{J_2^{\prime \prime }}}{}\mu ([F_1^{}F_2^{},G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })])\right)x^{1+\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })}.$$
(8)
Let us simplify the inner summation. Fix a part $`J_1^{\prime \prime }`$ and a part $`J_2^{\prime \prime }`$ and assume that $`\mathrm{crk}(G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime }))0`$. This excludes only the case when $`G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })=T`$.

Then $`G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })`$ is not a tree. Let $`K_1^{\prime \prime }`$ be the complement of $`J_1^{\prime \prime }`$ in $`I_1`$ and $`K_2^{\prime \prime }`$ be the complement of $`J_2^{\prime \prime }`$ in $`I_2`$.

Denote the trees $`F_1^{\prime \prime }[J_1^{\prime \prime }]`$ and $`F_2^{\prime \prime }[J_2^{\prime \prime }]`$ by $`T_1^{\prime \prime }`$ and $`T_2^{\prime \prime }`$. Then $`G`$ can be uniquely decomposed as

$$F_1^{\prime \prime }[K_1^{\prime \prime }]F_2^{\prime \prime }[K_2^{\prime \prime }](T_1^{\prime \prime }T_2^{\prime \prime })$$

and $`F_1^{}F_2^{}`$ can also be decomposed as

$$F_1^{}[K_1^{\prime \prime }]F_2^{}[K_2^{\prime \prime }](F_1^{}[J_1^{\prime \prime }]F_2^{}[J_2^{\prime \prime }]).$$

Hence the interval $`[F_1^{}F_2^{},G(F_1^{\prime \prime },J_1^{\prime \prime },F_2^{\prime \prime },J_2^{\prime \prime })]`$ is isomorphic to the product

$$[F_1^{}[K_1^{\prime \prime }],F_1^{\prime \prime }[K_1^{\prime \prime }]]\times [F_2^{}[K_2^{\prime \prime }],F_2^{\prime \prime }[K_2^{\prime \prime }]]\times [F_1^{}[J_1^{\prime \prime }]F_2^{}[J_2^{\prime \prime }],T_1^{\prime \prime }T_2^{\prime \prime }].$$

Choose enumerations $`J_1^{\prime \prime }(1),J_1^{\prime \prime }(2),\mathrm{},J_1^{\prime \prime }(k_1)`$ and $`J_2^{\prime \prime }(1),J_2^{\prime \prime }(2),\mathrm{},J_2^{\prime \prime }(k_2)`$ of the parts of parts of $`F_1^{\prime \prime }`$ and $`F_2^{\prime \prime }`$. Remark that $`k_1=\mathrm{crk}(F_1^{\prime \prime })+1`$ and $`k_2=\mathrm{crk}(F_2^{\prime \prime })+1`$. The inner sum can be restated as

$$\begin{array}{c}\underset{j=1}{\overset{k_1}{}}\underset{\mathrm{}=1}{\overset{k_2}{}}\mu ([F_1^{}[K_1^{\prime \prime }(j)],F_1^{\prime \prime }[K_1^{\prime \prime }(j)]])\mu ([F_2^{}[K_2^{\prime \prime }(\mathrm{})],F_2^{\prime \prime }[K_2^{\prime \prime }(\mathrm{})]])\hfill \\ \hfill \mu ([F_1^{}[J_1^{\prime \prime }(j)]F_2^{}[J_2^{\prime \prime }(\mathrm{})],T_1^{\prime \prime }(j)T_2^{\prime \prime }(\mathrm{})]),\end{array}$$

where $`T_1^{\prime \prime }(j)`$ and $`T_2^{\prime \prime }(\mathrm{})`$ are obvious notations.

As stated below in Corollary 4.5, it follows from the recursion hypothesis that for all special intervals $`[F^{\mathrm{}},T^{\mathrm{}}]`$ of smaller degree, one has

$$\mu ([F^{\mathrm{}},T^{\mathrm{}}])=(\mathrm{deg}([F_1^{\mathrm{}},T_1^{\mathrm{}}])+1)(\mathrm{deg}([F_2^{\mathrm{}},T_2^{\mathrm{}}])+1)\mu ([F_1^{\mathrm{}},T_1^{\mathrm{}}])\mu ([F_2^{\mathrm{}},T_2^{\mathrm{}}]).$$
(9)
Hence using this consequence of the recursion hypothesis, the inner sum is

$$\begin{array}{c}\underset{j=1}{\overset{k_1}{}}\underset{\mathrm{}=1}{\overset{k_2}{}}\mu ([F_1^{}[K_1^{\prime \prime }(j)],F_1^{\prime \prime }[K_1^{\prime \prime }(j)]])\mu ([F_2^{}[K_2^{\prime \prime }(\mathrm{})],F_2^{\prime \prime }[K_2^{\prime \prime }(\mathrm{})]])\hfill \\ \hfill ((\mathrm{deg}([F_1^{}[J_1^{\prime \prime }(j)],T_1^{\prime \prime }(j)])+1)(\mathrm{deg}([F_2^{}[J_2^{\prime \prime }(\mathrm{})],T_2^{\prime \prime }(\mathrm{})])+1)\\ \hfill \mu ([F_1^{}[J_1^{\prime \prime }(j)],T_1^{\prime \prime }(j)])\mu ([F_2^{}[J_2^{\prime \prime }(\mathrm{})],T_2^{\prime \prime }(\mathrm{})])),\end{array}$$

which in turn is equal to

$$(\mathrm{crk}(F_1^{})+1)(\mathrm{crk}(F_2^{})+1)\mu ([F_1^{},F_1^{\prime \prime }])\mu ([F_2^{},F_2^{\prime \prime }]).$$
(10)
Hence the third part (8) is equal, up to a polynomial in $`x`$ corresponding to special intervals with maximal element $`T`$, to

$$\begin{array}{c}\underset{\genfrac{}{}{0pt}{}{F_1^{}F_1^{\prime \prime }}{F_2^{}F_2^{\prime \prime }}}{}(1+\mathrm{crk}(F_1^{}))(1+\mathrm{crk}(F_2^{}))\mu ([F_1^{},F_1^{\prime \prime }])\mu ([F_2^{},F_2^{\prime \prime }])\hfill \\ \hfill x^{1+\mathrm{crk}(F_1^{})+\mathrm{crk}(F_2^{})}y^{\mathrm{crk}(F_1^{\prime \prime })+\mathrm{crk}(F_2^{\prime \prime })},\end{array}$$
(11)
which is $`x_x(xM_1)_x(xM_2)`$.

Therefore the full sum $`M`$ is equal to the expected formula, up to a polynomial in $`x`$. By Lemma 4.2 the value of $`M`$ at $`y=1`$ is $`1`$, and the value of the right-hand-side of Formula (7) at $`y=1`$ is also $`1`$. Hence Formula (7) stands exactly. The recursion step is done and the theorem is proved.

###### Corollary 4.5

The characteristic polynomial of the interval $`[F,T]`$ (denoted by $`\chi `$) depends only on the characteristic polynomials of the intervals $`[F_1,T_1]`$ and $`[F_2,T_2]`$ (denoted by $`\chi _1`$ and $`\chi _2`$). One has

$$\chi (y)=(y(\mathrm{deg}_1+1)(\mathrm{deg}_2+1))\chi _1(y)\chi _2(y),$$
(12)
where $`\mathrm{deg}_1=\mathrm{deg}([F_1,T_1])`$ and $`\mathrm{deg}_2=\mathrm{deg}([F_2,T_2])`$. As a special case, one has

$$\mu =(\mathrm{deg}_1+1)(\mathrm{deg}_2+1)\mu _1\mu _2$$
(13)
for Möbius numbers.

### 4.4 Factorization of characteristic polynomials

Let $`F,F^{}`$ be forests on the set $`I`$ with $`FF^{}`$. Let $`V`$ be the image of $`V(F)`$ in $`V(F^{})`$. Let us call marked vertices the elements of $`V`$. To each non-marked vertex $`vV(F^{})V`$, there correspond two subtrees $`T_1`$ and $`T_2`$. Let $`d_1`$ (resp. $`d_2`$) be the number of leaves of $`T_1`$ (resp. $`T_2`$) minus the number of marked vertices of $`T_1`$ (resp. $`T_2`$). One associates to the non-marked vertex $`v`$ its exponent which is the integer $`d_1d_2`$. The exponents of the pair $`(F,F^{})`$ are the exponents of the non-marked vertices of $`F^{}`$.

Remark that the exponents of $`(F,F^{})`$ only depend on $`F^{}`$ and the set $`V`$ of marked inner vertices, not on which $`F`$ is mapped to $`F^{}`$ using $`V`$.

###### Theorem 4.6

The characteristic polynomial of the interval $`[F,F^{}]`$ has only positive integer roots, which are the exponents of the pair $`(F,F^{})`$.

* Proof. The proof is by recursion on the cardinal of $`I`$ and $`\mathrm{deg}([F,F^{}])`$.

The statement is true for $`\mathrm{deg}([F,F^{}])=0`$ or $`I`$ a singleton, in which cases the set of exponents is empty.

If $`F^{}`$ is not a tree, then using Prop. 2.1, the statement is a consequence of the recursion hypothesis.

If $`F^{}`$ is a tree and $`V`$ contains the bottom vertex of $`F^{}`$, then the statement follows from the recursion hypothesis by using Prop. 2.3.

If $`F^{}`$ is a tree and $`V`$ does not contain the bottom vertex of $`F^{}`$, then the statement follows from the recursion hypothesis by using Corollary 4.5.

The theorem is proved.

Some more examples are given in Figure 5.

## 5 Partitive posets

### 5.1 Definition and product

A partitive poset is a ranked poset $`P`$ with $`\widehat{0}`$ and $`\widehat{1}`$ together with a ranked-poset map $`f_P`$ from $`P`$ to a subposet of the partition lattice of a finite set $`I`$ (possibly with shifted rank function).

The only examples which will be used here are all intervals $`[F,F^{}]`$ where $`F`$ and $`F^{}`$ are forests on $`I`$ with the map defined by the partition of the label set according to trees.

One can define the product of two partitive posets $`(P_1,I_1,f_1)`$ and $`(P_2,I_2,f_2)`$. As a ranked poset, it is the usual product $`P_1\times P_2`$. The composition of $`f_1\times f_2`$ with the inclusion map of partition lattices (induced by disjoint union of partitions) defines a poset map from $`P_1\times P_2`$ to the partition lattice of $`I_1I_2`$.

###### Proposition 5.1

The interval $`[F_1F_2,F_1^{}F_2^{}]`$ is isomorphic as a partitive poset to the product of $`[F_1,F_1^{}]`$ and $`[F_2,F_2^{}]`$.

* Proof. This is an easy reformulation of Prop. 2.1.

### 5.2 Twisted product of partitive posets

Consider two partitive posets $`P_1,P_2`$ such that their respective $`\widehat{1}`$ are mapped to a partition with only one part.

Choose for each of these posets a part of the image of their $`\widehat{0}`$ in the corresponding partition lattice. These chosen parts are denoted by $`K_1`$ and $`K_2`$.

The twisted product of $`P_1`$ and $`P_2`$ is defined as follows. As a poset, it is simply $`P_1\times P_2`$. The map to a partition lattice differs from the map for the usual product by gathering the parts containing $`K_1`$ and $`K_2`$ to a single part.

It is easy to see that, up to isomorphism of partitive poset, this construction does not depend on the choices made.

Let $`F`$ be a forest and $`T`$ be a tree on the set $`I`$ with $`FT`$. The binary tree $`T`$ defines a partition $`I=I_1I_2`$ and two subtrees $`T_1`$ on $`I_1`$ and $`T_2`$ on $`I_2`$. Assume that the image of $`V(F)`$ contains the lowest inner vertex of $`T`$. Recall the notations of 2.3.

###### Proposition 5.2

The interval $`[F,T]`$ is isomorphic as a partitive poset to the twisted product of the intervals $`[F_1,T_1]`$ and $`[F_2,T_2]`$.

* Proof. This is an easy reformulation of Prop. 2.3.

### 5.3 The $``$-product of partitive posets

Consider two partitive posets $`P_1,P_2`$ such that their respective $`\widehat{1}`$ are mapped to a partition with only one part.

The $``$ product of $`P_1`$ and $`P_2`$ is defined as follows. The underlying set is the disjoint union of $`P_1\times P_2`$ with elements denoted by $`\{a_1a_2\}`$ and of the set $`\{G(a_1,J_1,a_2,J_2)\}`$ where $`a_1`$ and $`a_2`$ are elements of $`P_1`$ and $`P_2`$ respectively and $`J_1`$ and $`J_2`$ are parts of the image of $`a_1`$ and $`a_2`$.

The order relation is given by the following relations:

1. $`(a_1a_2)(a_1^{}a_2^{})`$ if $`a_1a_1^{}`$ and $`a_2a_2^{}`$.
2. $`G(a_1,J_1,a_2,J_2)G(a_1^{},J_1^{},a_2^{},J_2^{})`$ if $`a_1a_1^{}`$, $`a_2a_2^{}`$ and the part $`J_1^{}`$ (resp. $`J_2^{}`$) contains the part $`J_1`$ (resp. $`J_2`$).
3. $`(a_1a_2)G(a_1^{},J_1^{},a_2^{},J_2^{})`$ if $`a_1a_1^{}`$ and $`a_2a_2^{}`$.

The map to a partition lattice is defined as follows. An element $`a_1a_2`$ is mapped to the disjoint union of the partitions associated to $`a_1`$ and $`a_2`$. An element $`G(a_1,J_1,a_2,J_2)`$ is mapped to the partition obtained from the disjoint union of the partitions associated to $`a_1`$ and $`a_2`$ by gathering the two parts containing $`J_1`$ and $`J_2`$ to a single part.

The result is a partitive poset, called the $``$-product of $`P_1`$ and $`P_2`$.

Let $`F`$ be a forest and $`T`$ be a tree on the set $`I`$. Assume that $`FT`$ and the image of $`V(F)`$ in $`V(T)`$ does not contain the lowest inner vertex of $`T`$. We keep the notations of section 2.4.

###### Proposition 5.3

The interval $`[F,T]`$ is isomorphic as a partitive poset to the $``$-product of the intervals $`[F_1,T_1]`$ and $`[F_2,T_2]`$ .

* Proof. This is essentially a reformulation of Prop. 2.4.

### 5.4 Marked trees

Let $`F,F^{}`$ be forests on the set $`I`$ with $`FF^{}`$.

###### Theorem 5.4

Up to isomorphism of partitive posets, the interval $`[F,F^{}]`$ depends only on the pair $`(F^{},V)`$ where $`V`$ is the subset of marked inner vertices of $`F^{}`$ associated to $`F`$.

* Proof. By recursion on the degree of $`[F,F^{}]`$ and the cardinal of $`I`$. This is clear if the degree is zero or the cardinal of $`I`$ is one.

If $`F^{}`$ is not a tree, then the proposition follows from the recursion hypothesis and Prop. 5.1.

If $`F^{}`$ is a tree and $`V`$ contains the lowest inner vertex of $`F^{}`$, the statement follows from the recursion hypothesis and Prop. 5.2.

If $`F^{}`$ is a tree and $`V`$ does not contain the lowest inner vertex of $`F^{}`$, this follows from the recursion hypothesis and Prop. 5.3.


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# Experimental study of the Ca2 1S+¹S asymptote

## I Introduction

In our previous paper O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) we reported on an accurate determination of the Ca2 X$`{}_{}{}^{1}\mathrm{\Sigma }_{\mathrm{g}}^{+}`$ ground state potential energy curve (PEC) from Laser Induced Fluorescense (LIF) spectroscopy. The study was motivated by the rapid progress in the development of the Ca frequency standard G. Wilpers and T. Binnewies and C. Degenhardt and U.Sterr and J. Helmcke (2002) and the recent photoassociation spectroscopy data on the 1S$`{}_{0}{}^{}+_{}^{1}`$P1 asymptote Zinner et al. (2000). It was considered as the first step of a comprehensive investigation, which should provide a description of the X state for short and intermediate internuclear distances, thus enabling the precise determination of the long range part of the PEC, for example from photoassociation spectroscopy or from a molecular beam experiment.

The results of the LIF experiments, however, suggested that in the case of Ca2 it might be possible to make a reasonable description of the long range part of PEC already by means of a classical spectroscopy. Here we mean the shallow potential well of the Ca dimer, which lead to thermal population even of the highest rovibrational levels for normal working temperatures (1220 K), so that a single laser scheme could be applied for their excitation. Of great importance is also the possibility to extend the description of the PEC by a long range dispersive expansion already from 9.4 Å O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002).

For detecting transitions from ground state levels with $`v^{\prime \prime }>35`$ we applied the Filtered Laser Excitation (FLE) technique, which was used also by Hofmann et al. Hofmann and Harris (1986) for studying the A$`{}_{}{}^{1}\mathrm{\Sigma }_{\mathrm{u}}^{+}`$ excited state in Ca2. With this technique we collected spectroscopic information for about 24 highly excited levels of the X state with $`v^{\prime \prime }`$ up to 38. The outer classical turning point of the last observed level with $`v^{\prime \prime }=38`$ and $`J^{\prime \prime }=10`$ is at 20 Å and is located on the rotationally reduced potential only 0.2 cm-1 below the molecular asymptote.

Although the FLE resolution was limited by the Doppler broadening, we will demonstrate that combining the data from O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) and this experiment, it is possible to reduce the uncertainty of the experimentally determined long range coefficients, and especially C6 to an extent, to compare them with the results of the most recent theoretical predictions Porsev and Derevianko (2002); Moszynski (2001).

In section II we explain the experimental set up and discuss the achieved experimental resolution and uncertainties. Section III summarizes the methods for constructing of the PEC. Analysis of the experimental data are performed in section IV, where we employed a Monte Carlo simulation in order to determine the error limits of the fitted long range parameters of the PEC.

## II Experiment

The calcium dimers are obtained in a heat pipe oven already described in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002). The experiments are performed at helium or argon buffer gas under a typical pressure of $`2050`$ mbar and an oven temperature of 1220 K. Working with argon as buffer gas enables us to reduce the pressure to a lower value than with helium without reducing the life time of the heat pipe due to solid calcium closing the optical path. In the frequency range accessible by the lasers in our group the most favorable Franck-Condon factors between the levels close to the asymptote of the X$`{}_{}{}^{1}\mathrm{\Sigma }_{\mathrm{g}}^{+}`$ state and the levels of the B$`{}_{}{}^{1}\mathrm{\Sigma }_{\mathrm{u}}^{+}`$ state ($`v^{}=2`$) are less than $`10^2`$. In order to achieve a sufficient signal-to-noise ratio using Fourier transform spectroscopy a long term stability in the operation of the oven is needed which is not achievable with our present apparatus. In addition, as it was mentioned in Ref.O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002), the discrete fluorescence is accompanied by a strong background emission due to bound-bound-free and free-bound-free molecular transitions. To overcome this problems we chose the filtered laser excitation (FLE) technique for direct excitation of the levels close to the asymptote of the ground state.

A 1 m monochromator (GCA/McPherson Instruments) used as a narrow band pass filter of a typical window width 2 cm-1 is set on a strong line of the fluorescence progression when exciting a transition to a selected rotational level with $`v^{}=2`$ of the B state using a single mode dye laser (Coumarine 6). Then the laser operating around 550 nm (60 mW on the Ca2 sample) scans the frequencies of transitions from near asymptote levels of the ground state to the selected $`v^{}=2`$ level. Laser frequencies resonant with such transitions will result in fluorescence, which matches the transmission band of the filter and can be detected. The signal after the monochromator is recorded as a function of the laser wavelength by a photomultiplier (Hamamatsu, R928). Although many other transitions of the X-B system contribute to the absorption spectrum of Ca2 in the scanned spectral region, only excitations which decay into the selected frequency window will be registered. Thus this selective technique provides greatly simplified absorption spectra in a region where the weak transitions from the asymptotic levels of interest are practically completely overlapped by other much stronger transitions.

The relative positions of the FLE lines are calibrated using the frequency comb of a temperature stabilized Fabry-Perot interferometer with a free spectral range of 149.75(1) MHz. The absolute line position is obtained using the absorption spectrum of iodine vapor at room temperature (fig. 1) calibrated with the IodineSpec calculating software with which the positions of the iodine lines are predicted with an accuracy better than 3MHz in the studied frequency range top ; H. Knöckel and E. Tiemann . In order to improve the signal-to-noise ratio each spectrum is recorded several times. Before the averaging procedure, the recorded signal is normalized to the laser intensity to minimize the influence of its variations with frequency and time. The typical width of the observed lines is 0.05 cm-1 corresponding to the Doppler broadening. The intensity of the slowly varying background due to free-bound-free or free-bound-bound transitions of the B-X system is comparable to the intensity of the strongest lines and is mainly responsible for the noise in the spectra. Taking account of the linewidth, the signal-to-noise ratio and the uncertainty in the calibration with the I2 lines, the uncertainty of the absolute frequency for the strongest lines is estimated to be 0.0035 cm-1. Two typical spectra are shown in fig.2 for low and intermediate $`J`$. The experimental traces as solid lines contain some gaps which were not scanned. The number above the line gives $`v^{\prime \prime }`$ and the inset gives $`v^{}`$ and $`J^{}`$ of the excited state.

Using the FLE technique we observed transitions from 44 ground state levels and among them 24 close to the asymptote with $`v^{\prime \prime }35`$. The last observed levels are ($`v^{\prime \prime }=38`$, $`J^{\prime \prime }=6,8,10`$) as summarized in the data field in fig. 3. The assignment of the new observed lines is performed using the potential energy curve determined in our previous study of the ground state O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) and a numerical potential of the B state determined from the data available in the literature Balfour and Whitlock (1975). Simulations of the transitions by these potentials for selected detection windows are presented in figure 2 as dotted lines. These lines are shifted vertically with respect to the observed traces in order to show clearly the quality of the simulation. The intensity of the synthetic spectrum is determined by the appropriate Franck-Condon factors, by the thermal population of the ground state levels and by the selected detection window. The small differences between the observed and the simulated spectral features could be attributed to the limited accuracy of the B state PEC (0.05 cm-1) and to the fact that the used ground state potential was determined for levels with only $`v^{\prime \prime }35`$. Also, only transitions in the main calcium isotopomer, 40Ca2 were simulated. The unambiguity of the assignment was usually proved further by the observation of relatively long (5-6 vibrational quanta) and self consistent vibrational progressions of P,R doublets.

With the present set-up we can study the influence of the collisions between calcium dimers and the buffer gas by changing its pressure since no additional instrumental broadening on the lines is present. We found that the collisional broadening and the shift of the observed lines are much smaller than what was previously assumed O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002). This means that the experimental uncertainties of the transitions obtained in that study were overestimated.

For completeness we enriched our data with progressions obtained by LIF using the 501 nm, 488 nm and 457 nm lines of an Argon ion laser (Spectra Physics, BeamLok 2060) recorded by Fourier transform spectroscopy. Most of the transitions which are known to be excited by these lines Vidal (1980) were observed in this study. The present set of transitions representing all the LIF and FLE data covers a range of rotational quantum numbers from $`J^{\prime \prime }=4`$ to $`164`$ and a range of vibrational quantum numbers from $`v^{\prime \prime }=0`$ to $`38`$. We have recorded a total of 3580 transitions resulting in 924 levels of the ground state 111See EPAPS Document No. … for the list of the transition frequencies. This document may be retrieved via the EPAPS homepage (http://www.aip.org/pubservs/epaps.html) or from ftp.aip.org in the directory /epaps/. See the EPAPS homepage for more information.

During this study six atomic calcium lines were also observed around $`1.9\mu `$m, which correspond to the 3D$`{}_{1,2,3}{}^{}^3`$P1,2,3 transitions, when irradiating the sample by Ar+ laser lines. These transitions have been already observed in Mg in a similar experiment Scheingraber and Vidal (1977). Here they could be attributed to predissociation of the molecular B state through a coupling with repulsive states correlated to the 3D + 1S asymptotes. It is worth mentioning that the 3D$`{}_{1,2,3}{}^{}^3`$P1,2,3 transitions were observed also at temperatures down to 950 K, which suggests that the first step of the process is predominantly excitation of pairs of free Ca atoms by the laser radiation to the molecular B state. The intensity ratio between the infrared emission and the laser light was highest for the 457 nm Ar+ line and decreases with the increase of the laser wavelength.

After a new examination of the previous Fourier transform spectra using the new potential energy curve which will be presented in the following, three unassigned weak molecular progressions were found to belong to the calcium isotopomer 44Ca40Ca. The exciting transitions were identified as (0, 42)$``$(4, 43) and (0, 72)$``$(5, 73) at 18788.36 cm-1 and (0, 111)$``$(8, 112) at 18787.36 cm-1.

## III Construction of PEC

Following the approach adopted in the previous report O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002), information which concerns only the ground state was extracted from the raw spectroscopic data. From transition frequencies with a common upper state level, differences between ground state levels were calculated. The PEC for the ground state was then constructed, which describes these experimentally observed differences. Similar to Ref.O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) the possible combinations of line frequencies within a progression were restricted only to pairs of one P and one R lines, forming a total of 8500 differences.

The methods for construction of PEC were discussed in detail in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) and will be summarized only briefly here.

The first method represents the potential as a truncated expansion over analytic functions:

$$U(R)=\underset{i=0}{\overset{n}{}}a_i\left(\frac{RR_m}{R+bR_m}\right)^i,$$
(1)
where $`a_i`$, $`b`$ and $`R_m`$ are parameters ($`R_m`$ is close to the equilibrium distance). For short and long internuclear distances the potential is smoothly extended respectively for $`RR_{\mathrm{inn}}`$ with

$$A+B/R^{12}$$
(2)
and for $`RR_{\mathrm{out}}`$ with

$$D_\mathrm{e}C_6/R^6C_8/R^8C_{10}/R^{10}\text{.}$$
(3)
Here $`D_\mathrm{e}`$ is the value of the dissociation energy defined with respect to the minimum of the PEC. Since $`R_{\mathrm{out}}`$ is usually chosen within the region where the contribution of the exchange energy is negligible, no additional dumping (or cut off) functions for the dispersion coefficients are introduced.

Parameters $`a_i`$ and $`C_6`$ and $`C_8`$ are fitted in a nonlinear fitting procedure (for details see Samuelis et al. (2000)), while $`A`$, $`B`$, $`C_{10}`$ and $`D_\mathrm{e}`$ are adjusted by the program in order to ensure smooth connection between the extensions and the analytic form. $`R_m`$, $`b`$ and the connecting points $`R_{\mathrm{inn}}`$ and $`R_{\mathrm{out}}`$ are kept fixed to values, which allow fast convergence of the fitting routine.

The second method defines the PEC for short and intermediate internuclear distances as a set of points connected with cubic spline function. For large internuclear distances the same long range expansion as in (3) is used. The values of the potential $`U_i`$ in a preselected grid of points, $`D_\mathrm{e}`$, $`C_6`$, $`C_8`$ and $`C_{10}`$ are treated as fitting parameters. They are determined in an iterative fitting routine, which linearizes the problem by using a modified version of the inverted perturbation approach Pashov et al. (2000). The connecting point $`R_{\mathrm{out}}`$ is chosen in the following way. Initially, the PEC is constructed in a pointwise form up to 13 Å. Then only the long range parameters are fitted assuming that $`R_{\mathrm{out}}=9.5`$ Å. Although both sections of the PEC are determined independently, their shapes turn out to be almost identical between 9.5 Å and 13 Å. As a last step the $`C_{10}`$ coefficient of the long range expansion is slightly adjusted (the change does not exceed few percent) in order to fit best the shape of the pointwise potential between 9.4 Å and 10 Å. The crossing point of the pointwise and the long range curves is taken as $`R_{\mathrm{out}}`$. The new value of $`R_{\mathrm{out}}`$ differs from that which was used when fitting the long range parameters. Usually the change is small (typically 0.1 Å) and since the two sections are very close in this region, the effect of such a change on the quality of the fit is negligible. Of course, a second iteration could be performed with the new value of $`R_{\mathrm{out}}`$, but usually it is necessary only in the beginning, when the initial values of the fitting parameters are far from the best ones.

Before fitting the PEC to the new data set, the experimental errors of the data obtained by LIF were reanalyzed, since the value of the normalized standard deviation $`\sigma 0.45`$ given in the previous study (Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002)) signals their overestimation. The value of the uncertainty before was chosen to be 0.01 cm-1 for a strong LIF line in order to take into account possible frequency shifts due to collisions. Since the new FLE measurements showed that the probable influence of the temperature and the buffer gas pressure are much smaller than expected we reduced the errors of all LIF frequencies by a factor of 0.6, which will give a more realistic estimate on the error limits of the fitted PEC parameters.

The analytic potential listed in table 1 describes the differences between the observed spectral lines from both experiments with a standard deviation $`\sigma =0.0064`$ cm-1 and normalized standard deviation $`\overline{\sigma }`$=0.69. The quality of the PEC for the near asymptotic levels is estimated by calculation the standard deviation with a reduced set of differences, where for each difference at least one level belongs to $`v^{\prime \prime }35`$. We obtained $`\sigma _{35}=0.0092`$ cm-1 and $`\overline{\sigma }_{35}=0.92`$. The same parameters for the numerical potential (table 2) are $`\sigma =0.0068`$ cm-1, $`\overline{\sigma }=0.74`$ and $`\sigma _{35}=0.0092`$ cm-1, $`\overline{\sigma }_{35}=0.89`$. In order to calculate the value of the pointwise potential in the range $`R<9.44`$ Å, a natural cubic spline through all the grid points should be used. The parameters of both curves are chosen such, that their minima are set to zero. In order to facilitate the comparison between the dissociation energies $`D_0`$ defined with respect to the lowest rovibrational level ($`v^{\prime \prime }=0,J^{\prime \prime }=0`$), their values are given in tables 1 and 2 as additional parameters.

## IV Uncertainties of the long range parameters

The motivation of this study is not only to describe the rovibrational structure of the 40Ca2 ground state. We rather want to examine to which extent the performed spectroscopic study is able to go beyond the reproduction of the observed differences between ground state levels. Of greatest interest is the reliability of the determined long range parameters (and especially $`C_6`$) since they play an important role in phenomena involving two interacting cold Ca atoms in the ground state.

Our analysis relies on two main assumptions:

* the interaction between two Ca atoms can be described within an adiabatic picture, through a single channel model applying the one dimensional Schrödinger equation with an effective potential energy curve;
* the shape of the potential for internuclear distances $`R9.4`$ Å can be described with the long range expression (3), neglecting the exchange energy.

Due to the zero net electronic and nuclear spin in the case of 40Ca and the large energy separation between the ground state and the lowest excited states the first assumption seems to be well justified. The second one is supported by the expected small value of the exchange energy Radzig and Smirnov (1985); O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) at 9.5 Å and the dominant van der Waals character of the interaction.

Under these assumptions we ask the question: what are the variations of the PEC parameters around the fitted ones which are still in agreement with the experimental data?

In Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) the answer was given by plotting a contour plot of the likehood function $`\chi ^2`$ by varying the long range parameters. For the nonlinear fitting procedures it is, however, not straightforward how to use the contour plot in order to determine the confidence interval of the parameters since it is not obvious to which confidence limit a given contour corresponds. That is why there is some ambiguity in the probable errors of the fitted parameters determined only by using contour plots. The use of the matrix of variances and covariances, which is obtained by the fitting routines in the linearized form is not useful in our case. The reason is that even if we assume the errors of the experimental frequencies being independent and following a normal distribution, the quantities which enter the fit are actually differences between these frequencies. Consequently their errors are not independent and we are not allowed to interpret the above mentioned matrix as in the case of independent data points.

A possible way to get the probability distribution of the fitted parameters is to perform a Monte Carlo simulation of synthetic data.

### IV.1 Monte Carlo simulation

Since our experimental data come with some measurement uncertainties, which we assume to be normally distributed, the set $`c^{(0)}`$ of the fitted parameters of the PEC will differ from the true one $`c^{(t)}`$. If we perform a series of similar experiments the experimental data sets will be slightly different and consequently we will obtain different sets of fitted parameters $`c_{exp}^{(i)}`$. Having a sufficient number of measurement sets we could plot the distribution of $`c_{exp}^{(i)}`$ and then decide what are the most probable values and what are their uncertainties.

So let us assume that the fitted potential $`U^{(0)}(R)`$, described with a set of parameters $`c^{(0)}`$, is not too far from the true one. Then, knowing the experimental uncertainty associated with each observed transition frequency, we can synthesize a set of experimental data which will have exactly the same structure as the real one (measurement errors, distribution of $`v`$ and $`J`$ quantum numbers). For this goal transition frequencies are formed using the eigenvalues for $`U^{(0)}(R)`$ (since the upper state levels play no role in our analysis their energies could be set to zero) and adding to each calculated frequency a small random quantity normally distributed with mean value zero and a standard deviation equal to the experimental error. Then we transform the synthetic frequencies into synthetic differences and use the same fitting procedure in order to obtain a new set of parameters $`c_{sim}^{(i)}`$. Performing a large number of simulations we can plot the distribution of $`c_{sim}^{(i)}c^{(0)}`$. Since the simulated data are related statistically to $`U^{(0)}(R)`$ in the same way as the real experimental data to the true potential and since these two potentials were assumed to be close to each other the obtained distribution should be not too different from that of $`c_{exp}^{(i)}c^{(t)}`$.

In order to realize these ideas we used the pointwise representation of the potential since in the present realization of our computer codes it allows more flexibility in connecting the long range expansion with the potential curve at intermediate internuclear distances. The prize to pay for this is that the first derivative of the PEC might have a small “kink” in $`R_{\mathrm{out}}`$. This problem, however, does not influence the analysis of the PEC and it could be avoided by slight adjustment of the pointwise curve. What we win is that all the long range parameters are fitted to the experimental data independently of the actual shape of the potential at intermediate internuclear distances. The continuity of the potential is ensured mainly by varying the connecting point $`R_{\mathrm{out}}`$ and to a smaller extend $`C_{10}`$. Analysis similar to those, performed in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) showed that the present body of experimental data fixes the inner part of the PEC approximately between 3.5 Å and 9.5 Å. Possible variations in this region are connected mainly with the experimental uncertainties and the influence of the selected representation for the potential is negligible. Therefore we may expect that the choice of the connecting point $`R_{\mathrm{out}}`$ around 9.5 Å makes our analysis almost independent of the functions used to model the PEC at short internuclear distances.

Having generated a set of synthetic differences $`\mathrm{\Delta }E_{v_1J_1,v_2J_2}^{(i)}=E_{v_1J_1}^{(i)}E_{v_2J_2}^{(i)}`$ we treat them as the experimental data. $`U^{(0)}(R)`$ is taken as initial potential and a small correction to it is fitted which should minimize the difference between $`\mathrm{\Delta }E_{v_1J_1,v_2J_2}^{(i)}`$ and the differences calculated with the corrected potential. The correction is defined as follows:

$$\delta U(R)=\underset{i=1}{\overset{N}{}}\delta u_iS_i(R)\text{, for R }<\text{ R}\text{out}$$
(4)
and

$$\delta U(R)=\delta D_e\frac{\delta C_6}{R^6}\frac{\delta C_8}{R^8}\frac{\delta C_{10}}{R^{10}}\text{, for R }\text{ R}\text{out}\text{,}$$
(5)
where $`S_i(R)`$ are defining functions of the pointwise potential (see Pashov (2000)), $`\delta u_i`$ are the values of the correction in an equidistant grid of internuclear distances $`R_i`$ and $`\delta D_e`$, $`\delta C_6`$, $`\delta C_8`$, $`\delta C_{10}`$ are the corrections to the long range parameters. Using the theory of perturbations the shift of the difference $`\mathrm{\Delta }E_{v_1J_1,v_2J_2}^{(i)}`$ due to $`\delta U(R)`$ can be written as:

$$\begin{array}{cc}\hfill \delta (\mathrm{\Delta }E_{v_1J_1,v_2J_2}^{(i)})=& \underset{i=1}{\overset{N}{}}\delta u_i(K_i^{v_1J_1}K_i^{v_2J_2})\hfill \\ \hfill +& \delta D_e(L_0^{v_1J_1}L_0^{v_2J_2})\hfill \\ \hfill & \underset{j=6,8,10}{}\delta C_j(L_j^{v_1J_1}L_j^{v_2J_2})\text{ ,}\hfill \end{array}$$
(6)
where

$$K_i^{vJ}=_0^{R_{out}}\mathrm{\Psi }_{vJ}^2(R)S_i(R)𝑑R$$
(7)
$$L_j^{vJ}=_{R_{out}}^{\mathrm{}}\mathrm{\Psi }_{vJ}^2(R)R^j𝑑R$$
(8)
are the corresponding mean values of $`S_i(R)`$ and $`R^j`$ calculated with the wave functions $`\mathrm{\Psi }_{vJ}(R)`$ of the levels forming the difference.

Note that in principle the exact presentation of $`U^{(0)}(R)`$ is not of importance since we study only the possible small variations around it which are still allowed by the experimental data. The advantage of expressing the correction to the potential in a pointwise form (cubic spline function is used for interpolation) is that the influence of the parameters $`\delta u_i`$ is localized in $`R`$, since away from $`R_i`$ $`S_i(R)`$ decays exponentially Pashov et al. (2000). This gives a high flexibility in constructing the needed form of the correction. Additionally, the correlations between $`\delta u_i`$ are introduced mainly by the experimental data and not by the selected basis functions.

With each set of simulated data a new fit is performed which adjusts $`\delta u_i`$, $`\delta D_e`$, $`\delta C_6`$, $`\delta C_8`$ and $`\delta C_{10}`$. Along with this we examine the contributions due to $`\delta u_i`$ and the long range corrections to the fitted differences (the sums in Eq. LABEL:fiteq). As it could be expected, the changes of the PEC for $`R<R_{out}`$ are very small ($`\delta u_i0.01`$ cm-1) for all sets of synthetic data due to the large amount of experimental observations in this region. In addition the corrections to the differences due to $`\delta u_i`$, i.e. the first term of the right side of eq. LABEL:fiteq, turn out to be smaller than the corresponding experimental uncertainties and in principle one could neglect them. We checked this and, indeed, the distribution of the long range parameters was almost identical for simulations with and without fitting $`\delta u_i`$. Since this is true for different numbers of $`\delta u_i`$ parameters, we may consider it as a proof of the statement made above, that in the present case the determination of the long range parameters is almost independent on the model used to describe the inner part of the PEC.

The positions of the energy levels and the molecular asymptote $`D_e`$ in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) were defined with respect to the minimum of the PEC, $`U_{\mathrm{min}}`$. Then we estimated that the possible variation of $`U_{\mathrm{min}}`$ for different representations of the potential is of the order of 0.01 cm-1, which was smaller than the uncertainty of the dissociation energy, 0.09 cm-1. With the extended experimental data set and after the revision of the experimental uncertainties we are now able to give a much better prediction of the dissociation energy with uncertainty also of the order of 0.01 cm-1. Obviously defining the dissociation energy with respect to $`U_{\mathrm{min}}`$ will introduce an undesired increase of the uncertainty for this long range parameter. Consequently, starting from here we will consider only the value of the dissociation energy $`D_0`$ defined with respect to the lowest rovibrational level $`E_{00}=E_{v^{\prime \prime }=0,J^{\prime \prime }=0}`$. Indeed, fitting $`\delta u_i`$ to the simulated data we convinced ourselves that although the shape of the potential (and also $`U_{\mathrm{min}}`$) could vary slightly from fit to fit, the overall effect on the position of $`E_{00}`$ is much smaller than the typical variation of $`U_{\mathrm{min}}`$. Nevertheless, the contribution of $`E_{00}`$ to the uncertainty of $`D_0`$ is taken into account.

In this way, the main steps of the performed Monte Carlo analysis are:

1. Find the PEC $`U^{(0)}(R)`$ which can reproduce the experimental observations with smallest standard deviation;
2. From the eigenvalues for $`U^{(0)}(R)`$ generate a set of synthetic data by adding normally distributed random deviations according the experimental uncertainties. This set has exactly the same structure as the experimental data;
3. Perform a fit with the synthetic data as it was done with the original one and collect the obtained potential parameters in a distribution list;
4. Repeat steps (2)-(4) until enough simulated long range parameters are collected in order to analyze their distribution.

### IV.2 Results

In figure 4 two projections of the long range parameters distribution obtained from 3000 simulations are shown. It is worth mentioning the strong correlation between $`C_6`$ and $`C_8`$, which is the case also for the other pairs of dispersive coefficients. In order to determine the confidence regions for the parameters we construct an ellipse in the four dimensional space of the parameters, whose axes have such orientations and relative lengths that the resulting surface follows the form of the distribution. Then we change gradually the lengths of the axes by a constant factor and count the number of points which are enclosed by the ellipse. For example, the ellipse which contains 68.3 % of the points will determine the 68.3 % (1$`\sigma `$) confidence region of the parameters. The projections of the 68.3 % and the 90 % confidence regions (strictly speaking the contours surrounding the projections) are plotted in the left part of figure 4 for the pair of parameters $`D_0`$ and $`C_6`$.

This allows us to determine the mean value and uncertainty of the dissociation energy of the 40Ca2 ground state with respect to the lowest rovibrational level as $`1069.868\pm 0.010`$ cm-1 and of the $`C_6`$ coefficient as $`(1.003\pm 0.033)10^7`$ cm-1Å6 at a confidence limit of 68.3 %. The values and the uncertainties of all the long range parameters are summarized in table 3 and compared with the values from other sources.

The highest observed rovibrational level in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) had $`v^{\prime \prime }=35`$ and it was concluded that with the available experimental data set it is not possible to give any reasonable estimation for $`C_6`$. Now, by using a Monte Carlo analysis we can be more rigorous. In figure 5 we compare the projections of two distributions on the $`D_0`$-$`C_6`$ plane. The first one is derived using only the data from Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) before the revision of those experimental errors. In order to obtain a meaningful estimation of the dissociation energy of the X state, we restricted in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) the possible variation of C6 within a $`\pm `$ 5 % interval around the theoretical value Porsev and Derevianko (2002). This interval is denoted in fig. 5 with horizontal dashed lines and leads to an uncertainty of the dissociation energy similar to that, given in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002). After including the new LIF and FLE data the distribution shrinks to the small black spot in the centre of figure 5 (see also the inset), which is actually the distribution from figure 4. It would be, however, not correct to interpret the drastic reduction of the size of the distribution only as a result of the transitions involving rovibrational levels with $`v^{\prime \prime }>35`$. In fact the items, which led to the distribution presented in figure 4 are:

* The assumption that the long range expansion (3) is valid starting from 9.4 Å. This allows to link the values of the long range parameters with the frequency differences involving levels with $`30v^{\prime \prime }38`$, i.e. the shape of the long range potential is roughly tested from 9.4 Å up to $`20`$ Å (the classical turning point of the last observed level). A Monte Carlo simulation shows (figure 6) the change of the distribution when shifting $`R_{\mathrm{out}}`$ from 9.4 Å only by 0.6 Å to $`R_{\mathrm{out}}=10`$ Å. Note, that in this case the loss of accuracy on $`C_6`$ is larger by a factor of two compared to the increase of the $`D_0`$ uncertainty;
* Availability of highly excited levels with $`v^{\prime \prime }=38`$, since they limit the variation of the dissociation energy;
* The enlargement of the experimental data, which allow accurate determination of the PEC for short and intermediate internuclear distances. Because of the large body of data, the long range parameters are almost independent of the exact representation of the rest part of the PEC, which is clearly indicated by the small variations of $`\delta u_i`$ (eq. LABEL:fiteq) during the statistical analysis;
* The corrected estimate of the experimental uncertainties of the data in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002).

### IV.3 The value of the $`C_6`$ coefficient

The confidence interval for $`C_6`$ given in this paper $`(1.003\pm 0.033)10^7`$ cm-1Å6 does not overlap with the most recent theoretical prediction of $`(1.070\pm 0.006)10^7`$ cm-1Å6 within the error stated in Ref. Porsev and Derevianko (2002).

From our side, we realize that an important point in our analysis is the assumption for the validity of the long range expansion (3) down to $`9.4`$ Å. As it was shown in fig. 6, shifting $`R_{\mathrm{out}}`$ to larger internuclear distances will increase the uncertainty on the fitted parameters. The same will happen if we introduce additional terms into the long range model (for example the exchange energy). Our analysis can readily include these additional parameters, provided there are new experimental observations which require this.

### IV.4 The s-wave scattering length

In order to obtain the s-wave scattering length and its confidence interval, it is straightforward to calculate its value for each of the simulated PEC. These calculations will show how reliably the spectroscopically determined potential up to $`20`$ Å can be applied to model cold collisions. The results are presented in fig. 7a. The position of the last bound level ($`v^{\prime \prime }=40`$) with respect to the molecular assymptote, $`D_0E_{v^{\prime \prime }=40,J^{\prime \prime }=0}`$ is shown in fig. 7b. The values of the scattering length $`a`$ within the 68.3 % confidence region vary from $`250a_0`$ to $`1000a_0`$ (the Bohr radius $`a_00.52918`$ Å). Since these values indicate a bound level very close to the asymptote (several MHz, see fig. 7b),initially we were surprised that from our much less accurate data (several 100 MHz) we can make such a good prediction of the position of the last bound level. Obviously the large amount of observed data fixes the accumulated phase of the wave function for this level along the PEC up to $`20`$ Å and the variation of the binding energy with respect to the asymptote is restricted mainly by the uncertainty of $`C_6`$. In addition, from figure 7b we see that the smaller the binding energy, the less sensitive it is to the uncertainties of the other long range parameters.

The inner wall of the potential ($`R<3.5`$ Å), however, is not well fixed by the experimental data. Could its change shift the last level by several MHz without influencing the positions of the other levels? The answer is negative. The wave functions for small internuclear distances for the highly excited levels differ only by a constant factor. For example, for a PEC with binding energy $`D_0E_{40}3`$ MHz for $`v^{\prime \prime }=40`$, the shapes of the wave functions for $`v^{\prime \prime }=40`$ and $`v^{\prime \prime }=35`$ are almost identical up to 7.5 Å and the ratio between them is:

$$\frac{\mathrm{\Psi }_{v^{\prime \prime }=35}(R)}{\mathrm{\Psi }_{v^{\prime \prime }=40}(R)}35\text{ for }R<7.5\text{ Å.}$$
(9)
So, using the perturbation theory it is clear, that a change of the potential for $`R<3.5`$ Å, which will shift the position of the level with $`v^{\prime \prime }=40`$ by 1 MHz will shift the level with $`v^{\prime \prime }=35`$ by $`1.2`$ GHz (0.04 cm-1). Since this change will not alter for example the position of the lowest level ($`v^{\prime \prime }=0`$), the introduced shift of the difference $`E_{v^{\prime \prime }=35}E_{v^{\prime \prime }=0}`$ will exceed the experimental uncertainty roughly by a factor of 6, which is a contradiction.

Due to the revised confidence interval for the $`C_6`$, the uncertainty of the scattering length was not reduced compared to Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) ($`112a_0÷800a_0`$), although the uncertainty of $`C_6`$ itself is smaller than the assumed one in Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) ($`\pm 5`$ % around the theoretical prediction of $`1.0710^7`$ cm-1Å6 Porsev and Derevianko (2002)). Following the dependence of the binding energy on the last level on $`C_6`$ (fig. 7b) we see that for smaller values of $`C_6`$ this level approaches the asymptote, which makes an accurate determination of the scattering length more difficult.

## V Conclusions

The 1S+1S molecular asymptote of the Ca dimer was studied by employing the filtered laser excitation technique. The spectroscopic data obtained in our previous study by Fourier transform spectroscopy were enriched by adding 56 transition frequencies from ground state levels with $`v^{\prime \prime }`$ up to 38. This gave us an opportunity to reanalyze the existing description of the long range part of the PEC from Ref. O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002).

By assuming the long range expansion (3) for the potential energy curve to be valid already from 9.4 Å, the probability distributions of the dissociation energy and the dispersion coefficients were derived from Monte Carlo analysis. Their mean values and uncertainties are given in Table 3. We showed, that due to the large amount of experimental data, the long range analysis is almost independent of the model functions used to describe the inner part of the PEC.

The reliability of the experimental potential for describing collisions between two Ca atoms at low temperatures was checked by calculating the s-wave scattering length and the position of the last bound level with respect to the asymptote for the variety of long range extensions of the potential allowed by the present experimental data. Following the distribution of the long range parameters, the binding energy of the last level was found to vary between several 10 kHz and several MHz. This confirmed our anticipations O. Allard and A. Pashov and H. Knöckel and E. Tiemann (2002) for a large and positive scattering length, $`250a_0<a<1000a_0`$. Contrary to the previous study, the present determination is purely experimental and does not rely on the theoretical estimations for C6. Moreover, the difference in the values of C6 from Ref. Porsev and Derevianko (2002) and from this study exceeds the stated uncertainties, although a small model dependence is still existing by altering the connecting point between the inner potential and the long range branch (compare fig. 6).

The Monte Carlo simulations open new perspectives for analyzing the uncertainties of the parameters of the PEC. They could be used also to determine the kind of spectroscopic data and their required accuracy for achieving the desired uncertainty of the fitted parameters. For example, we checked that including a vibrational progression up to $`v^{\prime \prime }=39`$ with the present experimental accuracy will not reduce the uncertainties of C6 and D0 significantly. This could be reached, however, even with the present distribution of data, provided the accuracy can be improved. Therefore, we believe that only high resolution Doppler free spectroscopic techniques should be used for further improvement on the Ca2 ground state PEC, especially at long internuclear distances.

## VI Acknowledgments

This work is supported by DFG through SFB 407. The authors appreciate the assistance of St. Falke during the experiments. A. P. gratefully acknowledges the research stipend from the Alexander von Humboldt Foundation.