RichMol: A general variational approach for rovibrational molecular dynamics in external electric fields

Abstract

A general variational approach for computing the rovibrational dynamics of polyatomic molecules in the presence of external electric fields is presented. Highly accurate, full-dimensional variational calculations provide a basis of field-free rovibrational states for evaluating the rovibrational matrix elements of high-rank Cartesian tensor operators, and for solving the time-dependent Schrödinger equation. The effect of the external electric field is treated as a multipole moment expansion truncated at the second hyperpolarizability interaction term. Our fully numerical and computationally efficient method has been implemented in a new program, RichMol, which can simulate the effects of multiple external fields of arbitrary strength, polarization, pulse shape and duration. Illustrative calculations of two-color orientation and rotational excitation with an optical centrifuge of NH${}_3$ are discussed.

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Cited by in corpus (16)

• The 2020 release of the ExoMol database: molecular line lists for exoplanet and other hot atmospheres
• Field-induced diastereomers for chiral separation
• Climbing the rotational ladder to chirality
• Exact quantum dynamics developments for floppy molecular systems and complexes
• First observation of electric-quadrupole infrared transitions in water vapour
• Electric quadrupole transitions in carbon dioxide
• Laser-induced dynamics of molecules with strong nuclear quadrupole coupling
• Detecting handedness of spatially oriented molecules by Coulomb explosion imaging
• Performance of a black-box-type rovibrational method in comparison with a tailor-made approach: case study for the methane-water dimer
• Coherent Control of the Rotation Axis of Molecular Superrotors
• Hyperfine-resolved rotation-vibration line list of ammonia (NH${}_3$)
• The effect of nuclear-quadrupole coupling in the laser induced alignment of molecules
• The nuclear-spin-forbidden rovibrational transitions of water from first principles
• Controlling rotation in the molecular-frame with an optical centrifuge
• Analyzing laser-induced alignment of weakly-bound molecular aggregates
• Methane dimer rovibrational states and Raman transition moments