Mixed quantum/classical theory (MQCT) approach to the dynamics of molecule-molecule collisions in complex systems.

We developed a general theoretical approach and a user-ready computer code that permit study of the dynamics of collisional energy transfer and ro-vibrational energy exchange in complex molecule-molecule collisions. The method is a mixture of classical and quantum mechanics. The internal ro-vibrational motion of collision partners is treated quantum mechanically using a time-dependent Schrödinger equation that captures many quantum phenomena including state quantization and zero-point energy, propensity and selection rules for state-to-state transitions, quantum symmetry and interference phenomena.

Rovibrational states calculations of the HO-HCN heterodimer with the multiconfiguration time dependent Hartree method.

Water and hydrogen cyanide are two of the most common species in space and the atmosphere with the ability of binding to form dimers such as HO-HCN. In the literature, while calculations characterizing various properties of the HO-HCN cluster (equilibrium distance, vibrational frequencies and rotational constants) have been done in the past, extensive calculations of the rovibrational states of this system using a reliable quantum dynamical approach have yet to be reported. In this work, we intend to mend that by performing the first calculation of the rovibrational states of the HO-HCN van der Waals complex on a recently developed potential energy surface.

Theoretical study of HCN-water interaction: five dimensional potential energy surfaces.

A new five-dimensional potential energy surface is calculated at the coupled-cluster CCSD(T) level of theory for the HCN-water system, treating both monomers as rigid rotors. The associated methodology, which combines extensive ab initio calculations of moderate accuracy (CCSD(T)/AVDZ) and a fitting procedure involving a much lower angular coverage with more accurate ab initio calculations (CCSD(T)/CBS), is described in detail. This methodology provides a time-saving approach to compute quantitatively accurate potential energy surfaces with reasonable computational effort.

New potential energy surface for the HCS(+)-He system and inelastic rate coefficients.

A new high quality potential energy surface is calculated at a coupled-cluster single double triple level with an aug-cc-pV5Z basis set for the HCS(+)-He system. This potential energy surface is used in low energy quantum scattering calculations to provide a set of (de)-excitation cross sections and rate coefficients among the first 20 rotational levels of HCS(+) by He in the range of temperature from 5 K to 100 K. The paper discusses the impact of the new ab initio potential energy surface on the cross sections at low energy and provides a comparison with the HCO(+)-He system.

Mixed quantum/classical theory for inelastic scattering of asymmetric-top-rotor + atom in the body-fixed reference frame and application to the H₂O + He system.

The mixed quantum/classical theory (MQCT) for inelastic molecule-atom scattering developed recently [A. Semenov and D. Babikov, J.

Rotational quenching of H2O by He: mixed quantum/classical theory and comparison with quantum results.

The mixed quantum/classical theory (MQCT) formulated in the space-fixed reference frame is used to compute quenching cross sections of several rotationally excited states of water molecule by impact of He atom in a broad range of collision energies, and is tested against the full-quantum calculations on the same potential energy surface. In current implementation of MQCT method, there are two major sources of errors: one affects results at energies below 10 cm(-1), while the other shows up at energies above 500 cm(-1). Namely, when the collision energy E is below the state-to-state transition energy ΔE the MQCT method becomes less accurate due to its intrinsic classical approximation, although employment of the average-velocity principle (scaling of collision energy in order to satisfy microscopic reversibility) helps dramatically.

Rotational relaxation of CS by collision with ortho- and para-H2 molecules.

Quantum mechanical investigation of the rotationally inelastic collisions of CS with ortho- and para-H2 molecules is reported. The new global four-dimensional potential energy surface presented in our recent work is used. Close coupling scattering calculations are performed in the rigid rotor approximation for ortho- and para-H2 colliding with CS in the j = 0-15 rotational levels and for collision energies ranging from 10(-2) to 10(3) cm(-1).

Ro-vibrational relaxation of HCN in collisions with He: rigid bender treatment of the bending-rotation interaction.

We present a new theoretical method to treat atom-rigid bender inelastic collisions at the Close Coupling (RB-CC) level in the space fixed frame. The coupling between rotation and bending is treated exactly within the rigid bender approximation and we obtain the cross section for the rotational transition between levels belonging to different bending levels. The results of this approach are compared with those obtained when using the rigid bender averaged approximation (RBAA) introduced in our previous work dedicated to this system.

The interaction of He with vibrating HCN: potential energy surface, bound states, and rotationally inelastic cross sections.

A four-dimensional potential energy surface representing the interaction between He and hydrogen cyanide (HCN) subjected to bending vibrational motion is presented. Ab initio calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and mid-bond functions. The global minimum is found in the linear He-HCN configuration with the H atom pointing towards helium at the intermolecular separation of 7.

Potential energy surface and rovibrational energy levels of the H2-CS van der Waals complex.

Owing to its large dipole, astrophysicists use carbon monosulfide (CS) as a tracer of molecular gas in the interstellar medium, often in regions where H(2) is the most abundant collider. Predictions of the rovibrational energy levels of the weakly bound complex CS-H(2) (not yet observed) and also of rate coefficients for rotational transitions of CS in collision with H(2) should help to interpret the observed spectra. This paper deals with the first goal, i.