In honour of Prof. Mario Capitelli On the occasion of his 70th ... - CNR

F. Pirani et al. PCCP 10, 5489 (2008)

EXPERIMENTAL DATA

The analysis of several experimental data allowed:-­‐The proper formula(on of an Improved Lennard Jones (IL J) modelwhere-­‐The proper descrip(on of the V dependence on the molecular orienta8on;-­‐The discovery of scaling laws (correla8on formulas): mathema(cal rela(ons binding well depth and its loca(on with fundamental physical proper8es of the interac(ng partners (polarizability, total charge , charge distribu8on….)

Results of the analysis of the experimental data Scaling laws + ILJThe phenomenological method-­‐Predicts the behavior of complex systems-­‐Suggests new experiments -­‐Aims relevant theore(cal calcula(ons -­‐Helps to understand the nature of the intermolecular interac(on and to develop-­‐extend modeling

The inves(ga(on of complex systemsandThe Perugia–Bari join8ng ac8vity1) On the possibility of using model poten(als for collision integral calcula(ons of interest for planetary atmospheres (M. Capitelli et al. Chem. Phys. 338 (2007) 62);2) Classical transport collision integrals for a Lennard-­‐Jones like phenomenological model poten(al (A. Laricchiuta et al. Chem. Phys. Le+. 445 (2007) 133);3) Transport proper(es of high-­‐temperature Mars-­‐atmosphere components (A. Laricchiuta et al. Thermophysics Conference 39 th AIAA(2007) 1);4) From microscopic to macroscopic modeling of supersonic seeded atomic beam(S. Longo et al. Lecture Notes in Computer Sciences 5072 (2008) 1131);5) The role of electronically excited states on transport proper(es of air plasmas(A. Laricchiuta et al. Thermophysics Conference 40 th AIAA (2008) 127308);6) Transport proper(es of high-­‐temperature Jupiter-­‐atmosphere components(A. Laricchiuta et al. Thermophysics Conference 41 th AIAA (2009) 4257); 7) High temperature Mars atmosphere. Part I : transport cross sec(ons(A. Laricchiuta et al. Eur. Phys. J. D 54 (2009) 607);8) Collision integrals for interac(ons involving atoms in electronically excited states(A. Laricchiuta et al. J. Phys. Chem. A 113 (2009) 15250);9) Transport proper(es of high-­‐temperature Jupiter-­‐atmosphere components(A. Laricchiuta et . al. Physics of Plasmas 17 (2010) 112315).

On the role of charge transfer in the stabiliza(on of weakly bound complexes involving water and hydrogen sulphide moleculesF. Pirani, P. Candori, M.S. Pedrosa Mundim, L. Belpassi,F. Tarantelli, D. CappelleSiUniversità degli studi di Perugia ItalyThe mee(ng in honour of Mario Capitelli-­‐ Bari 31/01-­‐01/02 2011

Å 3Å 3

Å 3 Å 3Å 3Å 3

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Ra(o of the well deptsRa(o of the long range a:rac(on coefficients

Ab ini(o calcula(on of the op(mized energy at theequilibrium distanceAb ini(o calcula(on of the CCSD(T)/aug-­‐ccpVQZ op(mized distance Kr-­‐X as a func(on of the orienta(on angle

=electron density change

=electron density changeSee also JACS (2010) 13046132

In the water complex the C.T. is 50-­‐150% larger providing a more effec(ve stabiliza(on

CO 2 dimer poten(al energy surface: rigid monomersThe bond-­‐bond approach -­‐ PCCP, 10, 4281 (2008) **** JCP, 130, 034110 (2009)** present calcula(ons: aug-­‐cc-­‐pVTZ basis set + bond func(ons

CO 2 dimer poten(al energy surface: rigid monomersTest on second virial coefficient data

CO 2 dimer poten(al energy surface: flexible monomersOne monomer symmetric stretchingR, Å

CO 2 dimer poten(al energy surface: flexible monomersOne monomer asymmetric stretchingR, Å

CO 2 dimer poten(al energy surface: flexible monomersOne monomer bending: averaging over monomer rota(onαR, Å