Irén Simkó

Motivated by recent experiments, the laser‐induced alignment‐and‐orientation (A&O) dynamics of the prolate symmetric top CH 3 X (X = F, Cl, Br, I) molecules is investigated, with particular emphasis on the effect of halogen substitution on the rotational constants, dipole moments, and polarizabilities of these species, as these quantities determine the A&O dynamics. Insight into possible control schemes for preferred A&O dynamics of halogenated molecules and best practices for A&O simulations are provided, as well. It is shown that for accurate A&O ‐dynamics simulations it is necessary to employ large basis sets and high levels of electron correlation when computing the rotational constants, dipole moments, and polarizabilities. The benchmark‐quality values of these molecular parameters, corresponding to the equilibrium, as well as the vibrationally averaged structures are obtained with the help of the focal‐point analysis (FPA) technique and explicit electronic‐structure computations utilizing the gold‐standard CCSD(T) approach, basis sets up to quintuple‐zeta quality, core‐correlation contributions and, in particular, relativistic effects for CH 3 Br and CH 3 I. It is shown that the different A&O behavior of the CH 3 X molecules in the optical regime is mostly caused by the differences in their polarizability anisotropy, in other terms, the size of the halogen atom. In contrast, the A&O dynamics of the CH 3 X series induced by an intense few‐cycle THz pulse is mostly governed by changes in the rotational constants, due to the similar dipole moments of the CH 3 X molecules. The A&O dynamics is most sensitive to the B rotational constant: even the difference between its equilibrium and vibrationally‐averaged values results in noticeably different A&O dynamics. The contribution of rotational states having different symmetry, weighted by nuclear‐spin statistics, to the A&O dynamics is also studied.