TY - CHAP

T1 - Non-Markovian extension of the energy-corrected sudden approximation on binary collisions of linear molecules

AU - Buldyreva, Jeanna V.

AU - Kouzov, A.P.

PY - 2017/8/20

Y1 - 2017/8/20

N2 - Higher accuracy of spectroscopic data modeling of different gaseous media is urgently called by progress inatmospheric physics and gas diagnostics. This task demands development of flexible theoretical modelsapplicable to different processes induced by collisional relaxation. Such flexibility is inherent to the energycorrected sudden approximation (ECSA) introduced almost 40 years ago [1] but still retaining its popularity forfittings of congested spectral structures near the band centers. Its extended variants [2,3] are able to tackle thenon-Markovian collisional relaxation of arbitrary rank up to the far spectral wings but apply strictly to thesingle case of linear rotators perturbed by structureless particles. Here, we report rigorous non-MarkovianECSA relaxation matrix expressions obtained for collisions between pairs of linear molecules.For that, the ECSA scattering operators and the intermolecular potential W are expanded in series of scalartripolar spherical harmonics [4] whose arguments are orientations of three axes, two of the linear colliders andthe third one of the intermolecular separation. All relaxation characteristics can be obtained when the Fouriertransforms of the ECSA time correlation functions are known. These transforms can be either calculated fromfirst principles or modeled using a priori information and accounting for the fundamental properties of therelaxation matrix. Besides, the ECSA spectral functions can be mimicked in terms of the leading spectralmoments which are readily obtained from the tripolar expansions of W and of the binary distribution function.The presented approach allows straightforward generalizations to collisions between any molecular tops whoserotation is substantially slower than the relative translational motion.References:[1] A.E. De Pristo, S.D. Augustin, R. Ramaswamy, and H. Rabitz, J. Chem. Phys. 71, 850 (1979) .[2] A. Kouzov, Phys. Rev.A 60, 2931 (1999).[3] J.V. Buldyreva and L. Bonamy, Phys. Rev.A 60, 370 (1999).[4] D. A. Varshalovich, A. N. Moskalev, and V. K. Khersonskii, Quantum Theory of Angular Momentum (WorldScientific, Singapore, 1988)

AB - Higher accuracy of spectroscopic data modeling of different gaseous media is urgently called by progress inatmospheric physics and gas diagnostics. This task demands development of flexible theoretical modelsapplicable to different processes induced by collisional relaxation. Such flexibility is inherent to the energycorrected sudden approximation (ECSA) introduced almost 40 years ago [1] but still retaining its popularity forfittings of congested spectral structures near the band centers. Its extended variants [2,3] are able to tackle thenon-Markovian collisional relaxation of arbitrary rank up to the far spectral wings but apply strictly to thesingle case of linear rotators perturbed by structureless particles. Here, we report rigorous non-MarkovianECSA relaxation matrix expressions obtained for collisions between pairs of linear molecules.For that, the ECSA scattering operators and the intermolecular potential W are expanded in series of scalartripolar spherical harmonics [4] whose arguments are orientations of three axes, two of the linear colliders andthe third one of the intermolecular separation. All relaxation characteristics can be obtained when the Fouriertransforms of the ECSA time correlation functions are known. These transforms can be either calculated fromfirst principles or modeled using a priori information and accounting for the fundamental properties of therelaxation matrix. Besides, the ECSA spectral functions can be mimicked in terms of the leading spectralmoments which are readily obtained from the tripolar expansions of W and of the binary distribution function.The presented approach allows straightforward generalizations to collisions between any molecular tops whoserotation is substantially slower than the relative translational motion.References:[1] A.E. De Pristo, S.D. Augustin, R. Ramaswamy, and H. Rabitz, J. Chem. Phys. 71, 850 (1979) .[2] A. Kouzov, Phys. Rev.A 60, 2931 (1999).[3] J.V. Buldyreva and L. Bonamy, Phys. Rev.A 60, 370 (1999).[4] D. A. Varshalovich, A. N. Moskalev, and V. K. Khersonskii, Quantum Theory of Angular Momentum (WorldScientific, Singapore, 1988)

M3 - Conference abstracts

SP - 64

BT - The 25th Colloquium on High Resolution Molecular Spectroscopy (HRMS 2017). August 20 - 25 2017. Helsinki. Finland.

Y2 - 20 August 2017 through 25 August 2017

ER -