mss10_Lecheng.ppt.pptVIP

* * * * * * * * * * * * * * A New Potential Energy Surface for N2O-He, and PIMC Simulations Probing Infrared Spectra and Superfluidity How precise need the PES and simulations be? Lecheng Wang, Daiqian Xie, Hui Li, Robert J. Le Roy and Piere-Nicholas Roy Open Questions for He-N2O Considering the Q3 asymmetry stretch of N2O alone gives a poor prediction of the vibrational shift for the He-N2O dimer. Predictions for large clusters require a PES which is accurate at long range, which ab initio calculation could not yield. nano droplet limit R. W. McKellar, J. Chem. Phys 127, 044315 (2007) Yanzi Zhou, Daiqian Xie, Donghui Zhang, J. Chem. Phys 124, 144317 (2006) There have been no quantitative theoretical studies of the evolution of ν3 the band origin shift (Δν3). N=1: theoretical estimate: 0.17 cm-1 experimental value: 0.25 cm-1 Open Questions for He-N2O In 4He nanodroplets the rotational constant of N2O is just half that of CO2 In the gas phase, B is similar for both. Both CO2 and N2O have 22 electrons, and have similar interactions with He. The only difference is monomer symmetry. The reason for the difference in the size dependence of B for N2O and CO2 clusters is unclear! K. Nauta and R.E. Miller, J. Chem. Phys 115, 10254 (2001) How to address these ‘tough’ problem?1. Get a highly precise N2O-vibration-dependent PES 2. Determine the band origin shift 3. Predict the superfluidity Part I: PES Part II: Δν3 Part III: fs Part I: The PES – How to describe stretching Hence, our ab-initio He-N2O PES must be 4D, depending on rNO, rNN, RHe-N2O and θ The strong coupling of Q1 and Q3 requires the symmetric stretch to be considered, and not just held fixed! A simple approach might be explicitly consider the asymmetric stretch coordinate while fixing the symmetric stretch coordinate How to incorporate asymmetric vibration of N2O? But … Δν for the dimer obtained in this way is only 0.189cm-1