# 1 Introduction

## 1 Introduction

The study of primordial chemistry of molecules adresses a number of interesting questions pertaining to the thermal balance of collapsing molecular protoclouds. In numerous astrophysical cases molecular cooling and heating influence dynamical evolution of the medium   
The existence of a significant abundance of molecules can be crucial on the dynamical evolution of collapsing objects. Because the cloud temperature increases with contraction, a cooling mechanism can be important for the structure formation, by lowering pressure opposing gravity, i.e. by allowing continued collapse of Jeans unstable protoclouds. This is particularly true for the first generation of objects.   
It has been suggested that a finite amount of molecules such as $`H_2`$, $`HD`$ and $`LiH`$ can be formed immediately after the recombination of cosmological hydrogen (Lepp and Shull 1984, Puy et al 1993). The cosmological fractional abundance $`HD/H_2`$ is small. Nevertheless, the presence of a non-zero permanent electric dipole moment makes $`HD`$ a potentially more important coolant than $`H_2`$ at modest temperatures, although $`HD`$ is much less abundant than $`H_2`$. Recently Puy and Signore (1997) showed that during the early stages of gravitational collapse, for some collapsing masses, $`HD`$ molecules were the main cooling agent when the collapsing protostructure had a temperature of about 200 Kelvins.   
Thus in section 2, we analytically estimate the molecular cooling during the collapse of protoclouds Then, in section 3, the possibility of thermal instability during the early phase of gravitational collapse is discussed.

## 2 Molecular functions of a collapsing protocloud

We consider here only the transition between the ground state and the first state. The transition is a dipolar transition whereas for $`H_2`$ molecule the transition is quadrupolar (because it has no permanent dipolar moment).   
In this study, we consider only the molecular cooling which is the dominant term in the cooling function as we have shown for a collapsing cloud (Puy & Signore 1996, 1997, 1998a, 1998b). we obtain for the cooling function of $`HD`$ the expression:

$$\mathrm{\Lambda }_{HD}\frac{3C_{1,0}^{HD}exp(\frac{T_{1,0}^{HD}}{T_m})h\nu _{1,0}^{HD}n_{HD}A_{1,0}^{HD}}{A_{1,0}^{HD}+C_{1,0}^{HD}\left[1+3exp(\frac{T_{1,0}^{HD}}{T_m})\right]}$$
(1)   
and the molecular cooling for the $`H_2`$ molecule is given by:

$$\mathrm{\Lambda }_{H_2}\frac{5n_{H_2}C_{2,0}^{H_2}A_{2,0}^{H_2}h\nu _{2,0}^{H_2}exp(\frac{T_{2,0}^{H_2}}{T_m})}{A_{2,0}^{H_2}+C_{2,0}^{H_2}\left[1+5exp(\frac{T_{2,0}^{H_2}}{T_m})\right]}$$
(2)   
The total cooling function is given by

$$\mathrm{\Lambda }_{Total}=\mathrm{\Lambda }_{HD}+\mathrm{\Lambda }_{H_2}=\mathrm{\Lambda }_{HD}(1+\xi _{H_2})$$
(3)   
where

$$\xi _{H_2}=\frac{\mathrm{\Lambda }_{H_2}}{\mathrm{\Lambda }_{HD}}$$

is the ratio between the $`H_2`$ and $`HD`$ cooling functions. Finally we deduce:

$$\mathrm{\Lambda }_{HD}\mathrm{\hspace{0.17em}2.66}\times 10^{21}n_{HD}^2exp(\frac{128.6}{T_m})\frac{\sqrt{T_m}}{1+n_{HD}\sqrt{T_m}\left[1+3exp(\frac{128.6}{T_m})\right]}$$
(4)   
$$\mathrm{\Lambda }_{H_2}\mathrm{\hspace{0.17em}1.23}\times 10^{20}n_{HD}^2exp(\frac{512}{T_m})\frac{\sqrt{T_m}}{5\times 10^4+n_{HD}\sqrt{T_m}\left[1+5exp(\frac{512}{T_m})\right]}$$
(5)   
and for the ratio:

$$\xi _{H_2}\mathrm{\hspace{0.17em}4.63}e^{\frac{383.4}{T_m}}\frac{1+\sqrt{T_m}n_{HD}[1+3exp(\frac{128.6}{T_m})]}{5\times 10^4+\sqrt{T_m}n_{HD}[1+5exp(\frac{512}{T_m})]}$$
(6)   
We study a homologous model of spherical collapse of mass $`M`$ similar to the model adopted in Lahav (1986) and Puy & Signore (1996) in which we only consider $`H_2`$ and $`HD`$ molecules. The aim of this paper is to analyse, through our approximations (where the only two first excited levels are considered), the evolution of the cooling and the potentiality of thermal instability.   
First, let us recall the equations governing dynamics of a collapsing protocloud:

$$\frac{dT_m}{dt}=2\frac{T}{r}.\frac{dr}{dt}\frac{2}{3nk}\mathrm{\Lambda }_{Total}$$
(7)   
for the evolution of the matter temperature $`T_m`$,

$$\frac{d^2r}{dt^2}=\frac{5kT_m}{2m_Hr}\frac{GM}{r^2}$$
(8)   
for the evolution of the radius $`r`$ of the collapsing cloud and

$$\frac{dn}{dt}=3\frac{n}{r}.\frac{dr}{dt}$$
(9)   
for the evolution of the matter density $`n`$.   
At the beginning of the gravitational collapse the matter temperature increases, then due to the very important efficiency of the molecular cooling, the temperature decreases. We consider here this transition regime i.e. the point where the temperature curve has a horizontal asymptot (see Puy & Signore 1997):

$$\frac{dT_m}{dt}=\mathrm{\hspace{0.17em}0}$$

Finally we obtain for the total molecular cooling

$$\mathrm{\Lambda }_{Total}=\delta T_m^{7/2}\frac{exp(5T_o/T_m)}{\left[1+\xi _oexp(\mathrm{\Delta }T_o/T_m)\right]^5}$$
(10)   
$`\delta =\frac{3kGM^2}{2m_H\kappa ^5}M^2`$ with $`\kappa =\mathrm{\hspace{0.17em}1.4}\times 10^{22}`$, $`T_o=128.6`$ K, $`\mathrm{\Delta }T_o=383.4`$ K and $`\xi _o=9260`$.

## 3 Thermal Instability

We have learned much about thermal instability in the last 30 years since the appearance of the work of Field (1965). Many studies have focused on the problem of thermal instabilitie in different situations. In general, astronomical objects are formed by self-gravitation. However, some objects can not explained by this process. For these objects the gravitational energy is smaller than the internal energy. Thus if the thermal equilibrium of the medium is a balance between energy gains and radiative losses, instability results if, near equilibrium, the losses increase with decreasing temprature. Then, a cooler than average region cools more effectively than its surroundings, and its temperature rapidly drops below the initial equilibrium value.   
Thus, if we introduce a perturbation of density and temperature such that some thermodynamics variable (pressure, temperature…) is held constant, the entropy of the material $`𝒮`$ will change by an amount $`\delta 𝒮`$, and the heat-loss function, by an amount $`\delta \mathrm{\Psi }=\mathrm{\Gamma }\mathrm{\Lambda }`$. From the equation

$$\delta \mathrm{\Psi }=Td(\delta 𝒮)$$

there is instability only if:

$$\left(\frac{\delta \mathrm{\Psi }}{\delta 𝒮}\right)>\mathrm{\hspace{0.17em}0}$$

We know that $`Td𝒮=C_pdT`$ in an isobaric perturbation. The corresponding inequality can be written:

$$\left(\frac{\delta \mathrm{\Psi }}{\delta T}\right)_p=\left(\frac{\delta \mathrm{\Psi }}{\delta T}\right)_n+\frac{n}{T}\left(\frac{\delta \mathrm{\Psi }}{\delta n}\right)_T<\mathrm{\hspace{0.17em}0}$$

which characterizes the Field’s criterion. The criterion involves constant $`P`$ because small blobs tend to maintain pressure equilibrium with their surroundings when heating and cooling get out of balance. In our case (i.e. at the transition regime), a thermal instability could spontaneously be developped if the Field’s Criterion is verified:

$$\frac{ln\mathrm{\Lambda }}{lnT_m}<\mathrm{\hspace{0.17em}0}$$
(11)   
In our case the logaritmic differential of the total molecular cooling function is given by

$$\frac{ln\mathrm{\Lambda }}{lnT_m}=\frac{7T_m+7T_m\xi _oe^{\frac{\mathrm{\Delta }T_o}{T_m}}10T_o10T_o\xi _oe^{\frac{\mathrm{\Delta }T_o}{T_m}}10\xi _o\mathrm{\Delta }T_oe^{\frac{\mathrm{\Delta }T_o}{T_m}}}{2+2\xi _oe^{\frac{\mathrm{\Delta }T_o}{T_m}}}$$
(12)   
In figure 1, we have plotted the curve $`y(T_m)=ln\mathrm{\Lambda }/lnT_m`$. It shows that the Field’s criterion is always verified.   
We conclude that a thermal instability is possible at the transition regime. Thus by maintening the same pressure in its surroundings, such a blob would get cooler and cooler and denser and denser until it could separate into miniblobs. This possibility is very interesting and could give a scenario of formation of primordial clouds. However, a quantitative study is necessary to evaluate the order of magnitude of the mass and the size of the clouds. This last point is crucial.   
Therefore, from these estimations, the calculations of molecular functions could, in principle, be extended to the $`CO`$ molecules for collapsing protoclouds at $`z<5`$ (see Puy & Signore 1998b). But, in any case -and in particular for the discussion of thermal instability at the transition regime\- the corresponding total cooling function must be numerically calculated because the excitation of many rotational levels must be taken into account. This extended study is beyond the scope of our paper.

## Acknowledgements

The authors gratefully acknowledge Stéphane Charlot, Philippe Jetzer, Lukas Grenacher and Francesco Melchiorri for valuable discussions on this field. Part of the work of D. Puy has been conducted under the auspices of the D<sup>r</sup> Tomalla Foundation and Swiss National Science Foundation

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