A general variational approach for computing rovibrational resonances of polyatomic molecules. Application to the weakly bound H2He+ and H2⋅CO systems

Dóra Papp; Tamás Szidarovszky; Attila G Császár

doi:10.1063/1.5000680

A general variational approach for computing rovibrational resonances of polyatomic molecules. Application to the weakly bound H₂He⁺ and H₂⋅CO systems

J Chem Phys. 2017 Sep 7;147(9):094106. doi: 10.1063/1.5000680.

Authors

Dóra Papp¹, Tamás Szidarovszky¹, Attila G Császár¹

Affiliation

¹ Laboratory of Molecular Structure and Dynamics, Institute of Chemistry, Eötvös Loránd University and MTA-ELTE Complex Chemical Systems Research Group, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary.

PMID: 28886650
DOI: 10.1063/1.5000680

Abstract

The quasi-variational quantum chemical protocol and code GENIUSH [E. Mátyus et al., J. Chem. Phys. 130, 134112 (2009) and C. Fábri et al., J. Chem. Phys. 134, 074105 (2011)] has been augmented with the complex absorbing potential (CAP) technique, yielding a method for the determination of rovibrational resonance states. Due to the effective implementation of the CAP technique within GENIUSH, the GENIUSH-CAP code is a powerful tool for the study of important dynamical features of arbitrary-sized molecular systems with arbitrary composition above their first dissociation limit. The GENIUSH-CAP code has been tested and validated on the H₂He⁺ cation: the computed resonance energies and lifetimes are compared to those obtained with a previously developed triatomic rovibrational resonance-computing code, D²FOPI-CCS [T. Szidarovszky and A. G. Császár Mol. Phys. 111, 2131 (2013)], utilizing the complex coordinate scaling method. A unique feature of the GENIUSH-CAP protocol is that it allows the simple implementation of reduced-dimensional dynamical models. To prove this, resonance energies and lifetimes of the H₂⋅CO van der Waals complex have been computed utilizing a four-dimensional model (freezing the two monomer stretches), and a related potential energy surface, of the complex.