Mid-holocene and last glacial maximum climate simulations with the IPSL model-part I: comparing IPSLCM5A to IPSLCM4

The climates of the mid-Holocene (MH), 6,000 years ago, and of the Last Glacial Maximum (LGM), 21,000 years ago, have extensively been simulated, in particular in the framework of the Palaeoclimate Modelling Intercomparion Project. These periods are well documented by paleo-records, which can be used for evaluating model results for climates different from the present one. Here, we present new simulations of the MH and the LGM climates obtained with the IPSL_CM5A model and compare them to our previous results obtained with the IPSL_CM4 model. Compared to IPSL_CM4, IPSL_CM5A includes two new features: the interactive representation of the plant phenology and marine biogeochemistry. But one of the most important differences between these models is the latitudinal resolution and vertical domain of their atmospheric component, which have been improved in IPSL_CM5A and results in a better representation of the mid-latitude jet-streams. The Asian monsoon’s representation is also substantially improved. The global average mean annual temperature simulated for the pre-industrial (PI) period is colder in IPSL_CM5A than in IPSL_CM4 but their climate sensitivity to a CO2 doubling is similar. Here we show that these differences in the simulated PI climate have an impact on the simulated MH and LGM climatic anomalies. The larger cooling response to LGM boundary conditions in IPSL_CM5A appears to be mainly due to differences between the PMIP3 and PMIP2 boundary conditions, as shown by a short wave radiative forcing/feedback analysis based on a simplified perturbation method. It is found that the sensitivity computed from the LGM climate is lower than that computed from 2 × CO2 simulations, confirming previous studies based on different models. For the MH, the Asian monsoon, stronger in the IPSL_CM5A PI simulation, is also more sensitive to the insolation changes. The African monsoon is also further amplified in IPSL_CM5A due to the impact of the interactive phenology. Finally the changes in variability for both models and for MH and LGM are presented taking the example of the El-Niño Southern Oscillation (ENSO), which is very different in the PI simulations. ENSO variability is damped in both model versions at the MH, whereas inconsistent responses are found between the two versions for the LGM. Part 2 of this paper examines whether these differences between IPSL_CM4 and IPSL_CM5A can be distinguished when comparing those results to palaeo-climatic reconstructions and investigates new approaches for model-data comparisons made possible by the inclusion of new components in IPSL_CM5A.

Gas-phase rate coefficients for the reactions of O(3P), S(3P), Se(3P), and Te(3P) with alkenes: application of perturbation frontier molecular orbital theory, correlations, and structure-activity relations (SARs)

The kinetics of the reactions of the atoms O(P-3), S(P-3), Se(P-3), and Te((3)p) with a series of alkenes are examined for correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes. These correlations may be employed to predict rate coefficients from the calculated HOMO energy of any other alkene of interest. The rate coefficients obtained from the correlations were used to formulate structure-activity relations (SARs) for reactions of O((3)p), S(P-3), Se (P-3), and Te((3)p) with alkenes. A comparison of the values predicted by both the correlations and the SARs with experimental data where they exist allowed us to assess the reliability of our method. We demonstrate the applicability of perturbation frontier molecular orbital theory to gas-phase reactions of these atoms with alkenes. The correlations are apparently not applicable to reactions of C(P-3), Si(P-3), N(S-4), and Al(P-2) atoms with alkenes, a conclusion that could be explained in terms of a different mechanism for reaction of these atoms.

On asymptotic behavior at infinity and the finite section method for integral equations on the half-line

e consider integral equations on the half-line of the form and the finite section approximation to x obtained by replacing the infinite limit of integration by the finite limit β. We establish conditions under which, if the finite section method is stable for the original integral equation (i.e. exists and is uniformly bounded in the space of bounded continuous functions for all sufficiently large β), then it is stable also for a perturbed equation in which the kernel k is replaced by k + h. The class of perturbations allowed includes all compact and some non-compact perturbations of the integral operator. Using this result we study the stability and convergence of the finite section method in the space of continuous functions x for which ()()()=−∫∞dttxt,sk)s(x0()syβxβx()sxsp+1 is bounded. With the additional assumption that ()(tskt,sk−≤ where ()()(),qsomefor,sassOskandRLkq11>+∞→=∈− we show that the finite-section method is stable in the weighted space for ,qp≤≤0 provided it is stable on the space of bounded continuous functions. With these results we establish error bounds in weighted spaces for x - xβ and precise information on the asymptotic behaviour at infinity of x. We consider in particular the case when the integral operator is a perturbation of a Wiener-Hopf operator and illustrate this case with a Wiener-Hopf integral equation arising in acoustics.