Issue 
A&A
Volume 536, December 2011



Article Number  A76  
Number of page(s)  11  
Section  Atomic, molecular, and nuclear data  
DOI  https://doi.org/10.1051/00046361/201118049  
Published online  12 December 2011 
Rotational excitation of 45 levels of ortho/paraH_{2}O by excited ortho/paraH_{2} from 5 K to 1500 K: statetostate, effective, and thermalized rate coefficients
^{1}
CAB, INTACSIC, Crta, Torrejón km 4, 28850 Torrejn de Ardoz, Madrid, Spain
^{2}
Observatoire de Paris, LUTH UMR CNRS 8102, 5 Place Janssen, 92195 Meudon, France
email: marielise.dubernet@obspm.fr
^{3}
Université Pierre et Marie Curie, LPMAA UMR CNRS 7092, Case 76, 4 Place Jussieu, 75252 Paris Cedex 05, France
^{4}
Institut UTINAM, UMR CNRS 6213, 41 bis avenue de l’Observatoire, BP 1615, 25010 Besançon Cedex, France
Received: 8 September 2011
Accepted: 10 October 2011
Aims. This work deals with the rotational excitation of ortho/paraH_{2}O with para/orthoH_{2} so that thermalized de(excitation) rate coefficients up to 1500 K for the first 45th level of ortho/paraH_{2}O are provided. Results are available in BASECOL with statetostate rate coefficients, their fitting coefficients, and effective rate coefficients. In addition, we provide a routine that combines all data in order to create thermalized rate coefficients.
Methods. Calculations were performed with the close coupling (CC) method over the whole energy range, using the same 5D potential energy surface (PES) as the one employed in previous papers. The current CC results were compared with thermalized quasiclassical trajectory (QCT) calculations using the same PES and with previous quantum calculations obtained between T = 20 K and T = 140 K with a different PES. The relative strengths of water excitation rate coefficients when water is excited with orthoH_{2} versus paraH_{2} was also analyzed.
Results. For collision with paraH_{2}, the rotationrotation process is found to be the dominant process for inelastic transfer for some water transitions, implying that calculations must include the j_{2} = 2 level. An important result of this paper is that j_{2} = 1 and j_{2} = 2 effective rate coefficients are very similar so that either j_{2} = 1 or j_{2} = 2 need to be calculated for astrophysical applications. In addition, at high temperature ratios of j_{2} = 2 (1) over j_{2} = 0, effective rate coefficients converge towards one to within a few percent. This study confirms that j_{2} = 3 effective rate coefficients are within 20% to j_{2} = 1 effective rate coefficients.
Conclusions. For astrophysical applications, these results imply that future collisional excitation of light molecules with H_{2} should be carried out with paraH_{2}, including j_{2} = 2, so as to obtain correct effective j_{2} = 0 effective rate coefficients and using the j_{2} = 2 effective rate coefficients for all excited j_{2} effective rate coefficients. In contrast, collisional excitation of heavy molecules with H_{2} might be restricted to paraH_{2} with j_{2} = 0 and to orthoH_{2} with j_{2} = 1, using the j_{2} = 1 rate coefficients for all excited j_{2} effective rate coefficients. These conclusions should simplify the future methodological choice for collisional excitation calculations applied to interstellar/circumstellar media.
Key words: molecular data / molecular processes / ISM: molecules
© ESO, 2011
1. Introduction
This is the fourth (Dubernet et al. 2006b, 2009; Daniel et al. 2010) and last publication from the largescale effort to obtain the highest possible accuracy for collisional excitation rate coefficients of H_{2}O with rotationally excited H_{2}. Those efforts are justified by the importance of water in various astrophysical media. Water is a key molecule for the chemistry and the energy balance of the gas in cold clouds and starforming regions, thanks to its relatively large abundance and large dipole moment. As the Heterodyne Instrument for the FarInfrared (HIFI) was launched in May 2009 on board the Herschel Space Observatory, publication of the water rate coefficients has become urgent. The instrument has observed the spectra of many molecules with unprecedented sensitivity with an emphasis on water lines in regions such as low or highmass starforming regions, protoplanetary disks, and AGB stars (van Dishoeck et al. 2011; Chavarría et al. 2010; Wyrowski et al. 2010; Bergin et al. 2010; Marseille et al. 2010; Kristensen et al. 2010; Decin et al. 2010). Interpreting these spectra relies upon the accuracy of the available collisional excitation rate coefficients that enter into the population balance of the emitting levels of the molecules. In the temperature range from 5 K to 1500 K, the most abundant collider likely to excite molecules in media with weak UV radiation fields is the hydrogen molecule, followed by the He atom.
The aim of the first paper (Dubernet et al. 2006b) was to study the influence of the new 5D potential energy surface (PES) determined by Faure et al. (2005) and Valiron et al. (2008). This accurate 5D PES, which is suitable for inelastic rotational calculations, was obtained from a 9D PES by averaging over H_{2} and H_{2}O ground vibrational states. As pointed out (Faure et al. 2005; Valiron et al. 2008), this stateaveraged PES is actually very close to a rigidbody PES using stateaveraged geometries for H_{2}O and H_{2}. Dubernet et al. (2006b) showed that this new PES (Faure et al. 2005; Valiron et al. 2008) led to a significant reevaluation of the rate coefficients for the excitation of H_{2}O by paraH_{2} (j = 0) below 20 K and to a weak effect with a maximum change of 40% for collisions with orthoH_{2} (j = 1) when their results were compared to the collisional calculations of Phillips et al. (1996), Dubernet & Grosjean (2002) and Grosjean et al. (2003) obtained with the 5D PES of Phillips et al. (1994). In addition, Dubernet et al. (2006b) provided rate coefficients for deexcitation of the lowest ten rotational levels of o/pH_{2}O by collisions with paraH_{2} (j_{2} = 0) and orthoH_{2} (j_{2} = 1) up to 20 K. This 5D PES has been used for all subsequent (Dubernet et al. 2009; Daniel et al. 2010) calculations, as well as for the present paper.
The second paper (Dubernet et al. 2009) provided statetostate rate coefficients among the 45 lowest levels of orthoH_{2}O with paraH_{2} (j_{2} = 0) and Δj_{2} = 0, + 2, as well as with j_{2} = 2 and Δj_{2} = 0, − 2. In addition to and only for the ten lowest energy levels of orthoH_{2}O have Dubernet et al. (2009) obtained statetostate rate coefficients involving j_{2} = 4 with Δj_{2} = 0, − 2 and j_{2} = 2 with Δj_{2} = + 2. The third paper (Daniel et al. 2010) provided statetostate rate coefficients among the 20 lowest levels of paraH_{2}O with H_{2} (j_{2} = 1) and Δj_{2} = 0, + 2, and among the ten lowest levels of paraH_{2}O with H_{2} (j_{2} = 3) and Δj_{2} = 0, − 2.
In those publications Dubernet et al. (2009), Daniel et al. (2010) carried out comparisons with thermalized QCT calculations of Faure et al. (2007) that shows large factors at intermediate temperatures and factors from 1 to 3 at high temperature for the strongest rate coefficients. We showed also that scaled collisional rate coefficients obtained with He could not be used in place of collisional rate coefficients with paraH_{2}. The quantum calculations of Dubernet et al. (2009) pointed out the importance of internal energy transfer between excitation of H_{2} and deexcitation of orthoH_{2}O, which was at the origin of some large differences observed with QCT calculations of Faure et al. (2007) and with scaled collisional rate coefficients obtained with He (Green et al. 1993). We recall that Faure et al. (2007) provides rate coefficients for rotational deexcitation among the lowest 45 rotational levels of o/pH_{2}O colliding with thermalized o/pH_{2} in the temperature range of 20 K to 2000 K. This set is a combination of various data: 1) data obtained with quasi classical trajectory (QCT) calculations with the H_{2} molecule assumed to be rotationally thermalized at kinetic temperature and calculated between 100 K and 2000 K; 2) the values at 20 K are CC calculations from Dubernet et al. (2006b) for the first five levels and equal to values at 100 K for all other levels; 3) scaled H_{2}OHe results from Green et al. (1993) for the weakest rate coefficients.
In this paper we provide information on two new systems, i.e. rotational excitation of the 45 lowest levels of orthoH_{2}O by orthoH_{2} leading to j_{2} = 1 effective rate coefficients for the 45 levels and to j_{2} = 3 effective rate coefficients for the lowest 5 levels. Indeed we provide a limited set of j_{2} = 3 effective rate coefficients for orthoH_{2}O because Daniel et al. (2010) found that ratios of paraH_{2}O effective rate coefficients were generally close to 1 within a maximum variation of 20%. The other new system is paraH_{2}OparaH_{2} where we provide j_{2} = 0 and j_{2} = 2 effective rate coefficients for the 45 and 20 lowest levels respectively. In addition, we complete the (Daniel et al. 2010) calculations providing j_{2} = 1 effective rate coefficients for rotational deexcitation from the 21rst (j_{τ} = 5_{2}) to the 45th (j_{τ} = 7_{6}) level of paraH_{2}O.
2. Methodology
2.1. Collisions with H_{2}
Our calculations provide statetostate collisional rate coefficients involving changes in both the target and the perturber rotational levels; i.e. where j_{1}τ_{1} and represent the initial and final rotational levels of water, j_{2} and the initial and final rotational levels of H_{2}, and T is the kinetic temperature.
The statetostate collisional rate coefficients are the Boltzmann thermal averages of the statetostate inelastic cross sections: (1)\arraycolsep1.75ptwhere E is the kinetic energy, k_{B} the Boltzmann constant and μ the reduced mass of the colliding system.
These statetostate collisional rate coefficients follow the principle of detailed balance, and reverse rate coefficients can be obtained from forward rate coefficients by the usual formula: (2)\arraycolsep1.75ptwhere g_{j1} and g_{j2} are the statistical weights related to rotational levels of H_{2}O and H_{2} respectively, and the different E_{int} are the rotational energies of the species.
Some astrophysical applications might use the socalled effective rate coefficients , which are given by the sum of the statetostate rate coefficients (Eq. (1)) over the final states of H_{2} for a given initial j_{2}: (3)%These effective rate coefficients do not follow the detailed balance principle, and both excitation and deexcitation should be calculated explicitly.
Finally, averaged deexcitation rate coefficients for ortho/paraH_{2}O by rotationally thermalized ortho/paraH_{2} can be obtained by averaging over the initial rotational levels of ortho/paraH_{2}: (4)with , where Z is the partition function over either ortho/paraH_{2} states. These averaged deexcitation rate coefficients are those directly calculated by Faure et al. (2007) with a QCT method.
2.2. Description of the calculations
In the current calculations we used the same expansion of the Faure et al. (2005), Valiron et al. (2008) 5D PES as in Dubernet et al. (2006b), where details can be found. For this PES, inaccuracies in inelastic cross sections might come from different sources: propagation parameters, description of the rotational Hamiltonians of the two molecules, sizes of H_{2}O and H_{2} rotational basis sets, and a level of approximation in quantum calculations where the coupled states (CS) approximation might be used instead of the exact close coupling (CC) method. Additional errors might be introduced in rate coefficients if the kinetic energy grid is not fine enough near thresholds, resulting in poor lowtemperature rate coefficients, or not extended to high enough energies, and leading to wrong hightemperature results.
Our quantum calculations were carried out with modified versions of the sequential and parallel versions of the MOLSCAT code (Hutson & Green 1994; McBane 2004). Identical to our previous publications the H_{2} energy levels are the experimental energies of Dabrowski (1984), and the H_{2}O energy levels and eigenfunctions were obtained by diagonalization of the effective Hamiltonian of Kyrö (1981), compatible with the symmetries of the PES. The energy levels of orthoH_{2}O and paraH2O can be found in Table 1 of (Dubernet et al. 2009), Table 1 of (Daniel et al. 2010), and in Green et al. (1993). The reduced mass of the system is 1.81277373 a.m.u.
Dubernet et al. (2009), Daniel et al. (2010) should be consulted for choosing an appropriate basis set. In the present calculations the ortho–H2OorthoH_{2} basis set is chosen to be B(n, 3) for the lowest 20 levels of ortho–H2O in order to be coherent with paraH2OorthoH_{2} calculations of Daniel et al. (2010). A B(n, 2) basis set is chosen for the paraH2OparaH_{2} calculations for the lowest 45 levels of paraH2O, and n corresponds to the number of water closed channels and is equal to ten. The basis set for paraH_{2} is limited to j_{2} = 2 because the j_{2} = 4 closed channel has a low overall effect (Dubernet et al. 2009), and because the j_{2} = 4 effective rate coefficients were very similar to the j_{2} = 2 effective rate coefficients in previous calculations (Dubernet et al. 2009). For rotational excitation from the 21st level to the 45th levels of either paraH_{2}O or orthoH_{2}O with orthoH_{2} a B(n, 1) basis set is used.
The CC calculations were carried out over essentially the whole energy range spanned by the Boltzmann distributions (Eq. (1)). The highest energy point calculated is at 8000 cm^{1}, and cross sections are extrapolated at higher energy in order to achieve convergence for deexcitation from the highest water energy levels. These extrapolations do not degrade the accuracy of rate coefficients because the concerned cross sections behave regularly. We carefully spanned the energy range above the inelastic channels and added more points in the presence of resonance structures. The energy steps were fixed to 0.1/0.2/0.5/1 cm^{1} for kinetic energy below 20/40/60/100 cm^{1}. Above a kinetic energy of 100 cm^{1} the steps were progressively increased from 1 cm^{1} to 500 cm^{1}. The thresholds’ grids were slightly relaxed for calculations above the 30th energy level.
We used the methodology described above to calculate sets of statetostate rate coefficients (Eq. (1)) described in Tables 1 and 2, in the temperature range from 5 K to 1500 K, for deexcitation among the 45 lowest levels of orthoH_{2}O/paraH_{2}O. From the calculated statetostate rate coefficients, the effective rate coefficients corresponding to j_{2} = 1, 3 for orthoH_{2}O and to j_{2} = 0, 1, 2 for paraH_{2}O can be calculated using Eq. (3). It should be noted that statetostate and effective rate coefficients are identical for the deexcitation from the 21st to 45th levels orthoH_{2}O/paraH_{2}O by orthoH_{2} because we use a B(n, 1) basis set in these calculations.
The BASECOL database (Dubernet et al. 2006a) provides full tables of the rate coefficient sets mentioned in Tables 1 and 2 i.e. sets (1) to (9). In these tables, the expected accuracy of the sets is given, as a function of the initial level of the deexcitation transition.
Rate coefficients available in BASECOL for orthoH_{2}OorthoH_{2}.
2.3. Accuracy of results
Apart from the usual checks of convergence with respect to propagation parameters, basis set, and total angular momentum, the statetostate rate coefficients have been carefully checked by detailed balance. It should be recalled that the quality of rate coefficients at low temperature is linked to the number of energy points close to the molecular thresholds, and we have an excellent energy grid for both j_{2} = 0, 2 (20 levels of paraH_{2}O) and j_{2} = 1 (20 levels of orthoH_{2}O).
The maximum values of the estimated errors are given in Table 1 for transitions starting from different levels of orthoH_{2}O and for the various sets of statetostate rate coefficients (1 to 2). Set (2a) shows very good accuracy for transitions among the first ten levels of orthoH_{2}O and for transitions from the 11th–20th levels to the first ten levels of orthoH_{2}O. Set (2b) has lower accuracy, but this is not a concern because this set does not contribute significantly to the effective rate coefficients. The accuracy of the effective rate coefficients (ER) reflects the accuracies of sets (1) and (2).
The maximum values of the estimated errors are given in Table 2 for transitions starting from different levels of paraH_{2}O and for the various sets of statetostate rate coefficients (5 to 9). Again the accuracy of the effective rate coefficients (ER) reflects the accuracies of sets (5) to (8).
3. Discussion
3.1. Influence of paraH_{2} excitation on CC effective rate coefficients
The results obtained for orthoH_{2}O (Dubernet et al. 2009) are confirmed in the present calculations. We find that the ratios can be very high for paraH_{2}O transitions for which no internal energy transfer occurs between H_{2} and paraH_{2}O; these high ratios are due to the strong longrange part of the PES for j_{2} = 2. This is particularly true for the weakest transitions for lowlying energy levels of paraH_{2}O (top left in Fig. 1) for which we observe ratios up to 80 at T = 20 K and commonly around 10 at 100 K. We note that those ratios diminish when the temperature increases. After the 45th transition, the ratios have a systematic behavior that is greater than one for deexcitation involving small rotational energy gaps, while smaller than one for the transitions with large energy gaps. This effect, particularly strong for the high rotational levels and for temperature below 400 K, reflects the strong rotationrotation energy transfer occurring for collisions with paraH_{2}. Indeed, deexcitation effective rate coefficients are strongly influenced by the corresponding statetostate rate coefficients for all paraH_{2}O α levels above the opening of the j_{2} = 2 level of H_{2}, while effective rate coefficients are mainly influenced by the statetostate rate coefficients.
Fig. 1
Ratios of effective deexcitation rate coefficients (Eq. (3)) / from the 1st to the 190th deexcitation transition and for: T = 20 K (black broken line), T = 100 K (black full line), T = 200 K (red), T = 400 K (green), T = 800 K (blue) and T = 1600 K (cyan). The abscissae indicate the labeling of the deexcitation transitions as indicated in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 
The relative strengths of the different collisional mechanisms: rotationtranslation, rotationrotation are illustrated through the behaviors of the statetostate cross sections in Fig. 2, for the deexcitation transitions from respectively the 4th, 7th, and 16th levels of paraH_{2}O. Very striking is the deexcitation from the 16th to the 2nd level (part 3a) where we note the strong contribution of the rotationrotation mechanism (red curve) over the full range of kinetic energies.
Fig. 2
Statetostate crosssections in Å^{2} as a function of relative kinetic energy (in cm^{1}) for the paraH_{2}O transitions: from level 4(2_{11}) to 1(0_{00}) 1a), to 2(1_{11}) 1b), to 3(2_{02}) 1c); from level 7(3_{22}) to 1(0_{00}) 2a), to 2(1_{11}) 2b), to 4(2_{11}); and from level 16(4_{40}) to 2(1_{11}) 3a), to 10(3_{31}) 3b), to 14(5_{24}) 3c), with the following paraH_{2} transitions: (black), (red), (green) and (blue). 
3.2. Analysis of orthoH_{2} to paraH_{2} ratios
An analysis can be conducted on the orthoH_{2} to paraH_{2} ratios of thermalized rate coefficients within CC calculations. Figure 3 illustrates that the orthoH_{2} to paraH_{2} ratios of paraH_{2}O thermalized CC rate coefficients go to one when the temperature increases for all transitions, implying that at high temperatures it is only necessary to calculate rate coefficients with one of the H_{2} species. This is explained by the ratios of the effective rate coefficients displayed in Figs. 4 to 8. This series of figures show that the ratios of effective rate coefficients / and / are similar for all transitions over the whole temperature range with a / ratio close to one within 35% at 200 K and about 20% at higher temperatures. We observe the same quantitative behaviors of the / ratios for the deexcitation from the 21st to 45th level of orthoH_{2}O.
The other ratios / and /, are close to one within 30–20%. All these ratios go to one to within a few percent when temperature increases, and this effect corresponds to a low influence by the potential well and by the longrange part of the PES on the dynamics of the collision. For the strongest collisional strengths, the orthoH_{2} to paraH_{2} ratios are in general close to one to better than 10% over the whole temperature range.
Fig. 3
Ratios of thermalized deexcitation rate coefficients (Eq. (4)) R(orthoH_{2}/paraH_{2}) from the 1st to the 190th deexcitation transition of paraH_{2}O and for the following temperatures: T = 20 K (back broken line), T = 100 K (black), T = 200 K (red), T = 400 K (green), T = 800 K (blue), and T = 1600 K (cyan). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 
Fig. 4
At T = 20 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 
Fig. 5
At T = 200 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicates the transition n → n − 1. 
Fig. 6
At T = 400 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 
Fig. 7
At T = 800 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 
Fig. 8
At T = 1600 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 
3.3. Comparison with H_{2}O + H_{2} effective rate coefficients of Phillips et al. (1996)
Comparison with effective rate coefficients of Phillips et al. (1996) can only be performed for the first ten levels of ortho/paraH_{2}O and for temperatures in the range 20 K to 140 K. It is recalled that between 20 K and 140 K, effective rate coefficients (Eq. (3)) for j_{2} = 1 are equal to orthoH_{2} thermalized rate coefficients (Eq. (4)) since j_{3} is barely populated, whereas thermalized rate coefficients (Eq. (4)) for paraH_{2} start to depart from the effective rate coefficients (Eq. (3)) for j_{2} = 0 around 140 K. The ratios of orthoH_{2}OorthoH_{2} (j_{2} = 1) effective rate coefficients given in Table 3 do not depend noticeably on temperature (The caption of corresponding table in Daniel et al. (2010) is wrong and should be the same as in Table 3). For the first transition of orthoH_{2}O the ratio is very close to one, in a similar way to what was found for the first transition of paraH_{2}O (Daniel et al. 2010). For the other transitions the new PES of Faure et al. (2005), Valiron et al. (2008) does not induce a significant change in rate coefficients for collision with orthoH_{2}.
Ratios of our effective o–H_{2}O/o–H_{2} rate coefficients for j_{2} = 1 over Phillips et al. (1996) rate coefficients.
The ratios of paraH_{2}OparaH_{2}j_{2} = 0 effective rate coefficients, given in Table 4, decrease slightly with temperature in a similar way to what was found for the orthoH_{2}O–paraH_{2} system (Note that the caption of corresponding table in Dubernet et al. 2009 is wrong and should be the same as in Table 4). As already mentioned in Dubernet et al. (2009), this certainly reflects the decreasing influence of the difference between the two different PES (Phillips et al. 1994; Faure et al. 2005) as temperature increases.
Ratios of the present paraH_{2} rate coefficients with Phillips et al. (1996)j_{2} = 0 effective rate coefficients.
3.4. Fitted rate coefficients
All statetostate rate coefficients listed in Table 2 and in Table 1 are fitted to an analytical form that is very similar to the one used by Mandy & Martin (1993): (5)with ϵ and {a_{k}}_{k ∈ [1;N] } being the fit coefficients. The fits were performed using numerical rate coefficients calculated at ~100 temperatures ranging from T_{min} to T_{max}, which are indicated in Tables 1 and 2. The fitted coefficients are such that the maximum error between initial data points and fitted values is minimized. A maximum value of N = 13 is needed for good accuracy over the full range of temperature. The fitted rate coefficients were subsequently compared to numerical rate coefficients calculated with a step of T = 1 K from T_{min} to T_{max}, and the maximum error found is less than 0.5%. We emphasize that these fits have no physical meaning, and are only valid in the temperature range of the relevant T_{min}, T_{max} and should not be used to perform extrapolations. The complete fitting coefficients (i.e. sets (1) to (4) of Table 1 and (5) to (9) of Table 2) are available in the BASECOL database (Dubernet et al. 2006a). The quality of the fits can be checked online through the graphic interface.
3.5. Thermalized rate coefficients and comparison with sets of Faure et al. (2007)
We provide a fortran routine^{1} that reads fitting coefficients of all statetostate rate coefficients calculated in the series of papers Dubernet et al. (2006b, 2009), Daniel et al. (2010), and in the present paper. This routine calculates deexcitation effective rate coefficients for the available possibilities and provides the thermalized deexcitation rate coefficients using both our available effective rate coefficients and guesses based on observations noted in our papers for the non calculated transitions. Table 5 provides an abstract of calculated and estimated effective rate coefficients. The scaling factor M lies between 0.8 and 1.2 for scaling between and , between and , it should be very close to 1 between and and between and . Indeed, we showed in (Daniel et al. 2010) that j_{2} = 3 significant effective rate coefficients are very close to j_{2} = 1, therefore we can safely assume all unknown j_{2} = 3,5,7 significant effective rate coefficients to be close to j_{2} = 1 in calculating the thermalized rate coefficients. We can make the same assumptions concerning all unknown j_{2} = 4,6,8 significant effective rate coefficients with respect to j_{2} = 2. In addition we showed in the current paper that the j_{2} = 2 and j_{2} = 1 effective rate coefficients are very similar. In BASECOL we propose a set of thermalized rate coefficient using M = 1.
Effective rate coefficients (ER) included in the thermalized rate coefficients.
Another possibility for high water levels is to directly use the set of rate coefficients published by Faure et al. (2007), but to be aware of their limitation. Indeed a large fraction of the transitions over a range of temperatures correspond to scaled H_{2}OHe results of Green et al. (1993) whereas QCT calculations correspond to the most significant rate coefficients (those above 10^{14}) included in the published sets (Faure et al. 2007). Comparisons between our averaged deexcitation rate coefficients and the QCT results (Faure et al. 2007) have already been performed in previous papers, and the same general conclusions apply to the present calculations. The CC and QCT rate coefficients are within a factor of 3 over the temperature range, whereas scaled He calculations mostly underestimate CC rate coefficients up to several orders of magnitude for the weakest transitions. In addition we note that at low temperatures orthoH_{2} to paraH_{2} ratios of thermalized CC rate coefficients behave differently in CC calculations compared to the published set of (Faure et al. 2007). Of course, the scaledHe rate coefficients of Green et al. (1993) included in the published set of Faure et al. (2007) give ratios equal to one. Nonetheless, the ratios involving the QCT rate coefficients differ from the ratios involving CC calculations.
4. Concluding remarks
We have concluded the work on the rotational excitation of ortho/paraH_{2}O by excited para/orthoH_{2} providing close coupling statetostate rate coefficients for the lowest 45 levels of ortho/paraH_{2}O. As indicated in Table 5 some effective rate coefficients need to be guessed for some transitions and range of temperature. The calculations of these missing effective rate coefficients would have been far too lengthy at the current level of accuracy, thus requiring the use of approximations leading to higher uncertainties in the results. We believe that the uncertainties generated in such approximate calculations would be close to the current guesses, and they are not particularly useful in the context of astrophysical applications. These are educated guesses based on conclusions drawn from comparisons performed between all our calculated sets of CC rate coefficients. Indeed our present results confirm that j_{2} = 3 calculations are about 20% of j_{2} = 1, as already been noted by Daniel et al. (2010). Another result of this paper is that j_{2} = 1 and j_{2} = 2 effective rate coefficients are very similar so that either j_{2} = 1 or j_{2} = 2 need to be calculated for astrophysical applications. Considering that, for some moleculeparaH_{2}, such as the H_{2}O systems, rotationrotation processes are important, it is preferable to carry out scattering calculations with paraH_{2} including j_{2} = 0, 2 in the basis set, so that the j_{2} = 0 effective rate coefficients are correctly reproduced. The effective j_{2} = 1 rate coefficients can then be taken as equal to the effective j_{2} = 2 rate coefficients. On the other hand, for heavy molecules with a high density of rotational states such as CS, SiS, SO_{2}, and heavier molecules rotationrotation processes is certainly not efficient with H_{2} and calculations might be restricted to paraH_{2} with j_{2} = 0 and to orthoH_{2} with j_{2} = 1.
In addition at high temperature we find that ratios of j_{2} = 2 (1) over j_{2} = 0 effective rate coefficients goes to one to within a few percent, implying that it is enough to calculate the j_{2} = 0 effective rate coefficients at high temperature. These conclusions should simplify the future methodology choice for the collisional excitation calculations applied to interstellar/circumstellar media.
For citation purposes, the use of each set of statetostate and related effective rate coefficients data should mention the corresponding collisional paper, the paper of the potential energy surface (Valiron et al. 2008), and the BASECOL database (Dubernet et al. 2006a or a more recent reference) which is the only reference for the numerical values. The use of any thermalized rate coefficients should refer to the potential energy surface (Valiron et al. 2008), and to the complete set of collisional papers (Dubernet et al. 2006b, 2009; Daniel et al. 2010) including the current reference and the BASECOL database (Dubernet et al. (2006a) or a more recent reference).
Acknowledgments
Most scattering calculations were performed at the IDRISCNRS and CINES under project 200607080910 04 1472. This research was supported by the CNRS national program “Physique et Chimie du Milieu Interstellaire” and by the FP6 Research Training Network “Molecular Universe”, contract Number: MRTNCT2004512302. BASECOL is supported by the ASTRONET EUFP7 Project and by VAMDC funded under the Combination of Collaborative Projects and Coordination and Support Actions Funding Scheme of The Seventh Framework Program. Call topic: INFRA20081.2.2 Scientific Data Infrastructure. Grant Agreement number: 239108. FD thanks Spanish MICINN for support under grant CONSOLIDER ASTROMOL CSD200900038 and CSIC for grant JAEDOC.
References
 Bergin, E. A., Hogerheijde, M. R., Brinch, C., et al. 2010, A&A, 521, L33 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Chavarría, L., Herpin, F., Jacq, T., et al. 2010, A&A, 521, L37 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Dabrowski, I. 1984, Canadian J. Phys., 62, 1639 [Google Scholar]
 Daniel, F., Dubernet, M., Pacaud, F., & Grosjean, A. 2010, A&A, 517, A13 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Decin, L., Agúndez, M., Barlow, M. J., et al. 2010, Nature, 467, 64 [NASA ADS] [CrossRef] [PubMed] [Google Scholar]
 Dubernet, M.L., & Grosjean, A. 2002, A&A, 390, 793 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Dubernet, M., Grosjean, A., Daniel, F., et al. 2006a, in Rovibrational Collisional Excitation Database: BASECOL – http://basecol.obspm.fr (Japan: Journal of Plasma and Fusion Research Series, series 7) [Google Scholar]
 Dubernet, M.L., Daniel, F., Grosjean, A., et al. 2006b, A&A, 460, 323 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Dubernet, M.L., Daniel, F., Grosjean, A., & Lin, C. Y. 2009, A&A, 497, 911 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Faure, A., Valiron, P., Wernli, M., et al. 2005, J. Chem. Phys., 122, 221102 [NASA ADS] [CrossRef] [PubMed] [Google Scholar]
 Faure, A., Crimier, N., Ceccarelli, C., et al. 2007, A&A, 472, 1029 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Green, S., Maluendes, S., & McLean, A. D. 1993, ApJS, 85, 181 [Google Scholar]
 Grosjean, A., Dubernet, M.L., & Ceccarelli, C. 2003, A&A, 408, 1197 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Hutson, J. M., & Green, S. 1994, MOLSCAT computer code,version 14 (United Kingdom: Collaborative Computational Project No. 6 of the Science and Engineering Research Council) [Google Scholar]
 Kristensen, L. E., Visser, R., van Dishoeck, E. F., et al. 2010, A&A, 521, L30 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
 Kyrö, E. 1981, J. Mol. Spectrosc., 88, 167 [NASA ADS] [CrossRef] [Google Scholar]
 Mandy, M. E., & Martin, P. G. 1993, ApJS, 86, 199 [NASA ADS] [CrossRef] [Google Scholar]
 Marseille, M. G., van der Tak, F. F. S., Herpin, F., et al. 2010, A&A, 521, L32 [Google Scholar]
 McBane, G. 2004, MOLSCAT computer code, parallel version (USA: G. McBane) [Google Scholar]
 Phillips, T. R., Maluendes, S., McLean, A. D., & Green, S. 1994, J. Chem. Phys., 101, 5824 [NASA ADS] [CrossRef] [Google Scholar]
 Phillips, T. R., Maluendes, S., & Green, S. 1996, ApJS, 107, 467 [NASA ADS] [CrossRef] [Google Scholar]
 Valiron, P., Wernli, M., Faure, A., et al. 2008, J. Chem. Phys., 129, 134306 [NASA ADS] [CrossRef] [PubMed] [Google Scholar]
 van Dishoeck, E. F., Kristensen, L. E., Benz, A. O., et al. 2011, PASP, 123, 138 [NASA ADS] [CrossRef] [Google Scholar]
 Wyrowski, F., van der Tak, F., Herpin, F., et al. 2010, A&A, 521, L34 [NASA ADS] [CrossRef] [EDP Sciences] [Google Scholar]
Appendix A: Fit coefficients
As said in Sect. 3.4, rate coefficients for the various symmetries of the H_{2}O/H_{2} collisional system are fitted to an analytical form. The fit coefficients are available in the Basecol database Dubernet et al. (2006a) and Tables A.1 and A.2 show a subset of the coefficients, for the actual collisional symmetries. The full tables can be found in the BASECOL database along with a program that enables statetostate, effective and thermalized rate coefficients to be computed from those coefficients.
Example of fit coefficients for the collisional system pH_{2}O/pH_{2}.
Example of fit coefficients for the collisional system oH_{2}O/oH_{2}.
All Tables
Ratios of our effective o–H_{2}O/o–H_{2} rate coefficients for j_{2} = 1 over Phillips et al. (1996) rate coefficients.
Ratios of the present paraH_{2} rate coefficients with Phillips et al. (1996)j_{2} = 0 effective rate coefficients.
All Figures
Fig. 1
Ratios of effective deexcitation rate coefficients (Eq. (3)) / from the 1st to the 190th deexcitation transition and for: T = 20 K (black broken line), T = 100 K (black full line), T = 200 K (red), T = 400 K (green), T = 800 K (blue) and T = 1600 K (cyan). The abscissae indicate the labeling of the deexcitation transitions as indicated in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 

In the text 
Fig. 2
Statetostate crosssections in Å^{2} as a function of relative kinetic energy (in cm^{1}) for the paraH_{2}O transitions: from level 4(2_{11}) to 1(0_{00}) 1a), to 2(1_{11}) 1b), to 3(2_{02}) 1c); from level 7(3_{22}) to 1(0_{00}) 2a), to 2(1_{11}) 2b), to 4(2_{11}); and from level 16(4_{40}) to 2(1_{11}) 3a), to 10(3_{31}) 3b), to 14(5_{24}) 3c), with the following paraH_{2} transitions: (black), (red), (green) and (blue). 

In the text 
Fig. 3
Ratios of thermalized deexcitation rate coefficients (Eq. (4)) R(orthoH_{2}/paraH_{2}) from the 1st to the 190th deexcitation transition of paraH_{2}O and for the following temperatures: T = 20 K (back broken line), T = 100 K (black), T = 200 K (red), T = 400 K (green), T = 800 K (blue), and T = 1600 K (cyan). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 

In the text 
Fig. 4
At T = 20 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 

In the text 
Fig. 5
At T = 200 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicates the transition n → n − 1. 

In the text 
Fig. 6
At T = 400 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 

In the text 
Fig. 7
At T = 800 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 

In the text 
Fig. 8
At T = 1600 K, ratios of effective deexcitation rate coefficients (Eq. (3)) from the 1st to the 190th deexcitation transition of paraH_{2}O: /(black), / (red), / (green), / (blue), and / (indigo). The abscissae indicate the labeling of the deexcitation transitions as given in Table 4 of Daniel et al. (2010). The arrows combined with their label “n” indicate the transition n → n − 1. 

In the text 
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