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The laser-induced alignment-and-orientation (A&O) dynamics of the prolatesymmetric top CH$_3$X (X = F, Cl, Br, I) molecules is investigated, withparticular emphasis on the effect of halogen substitution on the rotationalconstants, dipole moments, and polarizabilities of these species, as thesequantities determine the A&O dynamics. Insight into possible control schemesfor preferred A&O dynamics of halogenated molecules and best practices for A&Osimulations are provided, as well. It is shown that for accurate A&O-dynamicssimulations it is necessary to employ large basis sets and high levels ofelectron correlation when computing the rotational constants, dipole moments,and polarizabilities. The benchmark-quality values of these molecularparameters, corresponding to the equilibrium, as well as the vibrationallyaveraged structures are obtained with the help of the focal-point analysis(FPA) technique and explicit electronic-structure computations utilizing thegold-standard CCSD(T) approach, basis sets up to quintuple-zeta quality,core-correlation contributions and, in particular, relativistic effects forCH$_3$Br and CH$_3$I. It is shown that the different A&O behavior of theCH$_3$X molecules in the optical regime is mostly caused by the differences intheir 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 intensefew-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 ismost sensitive to the $B$ rotational constant: even the difference between itsequilibrium and vibrationally-averaged values results in noticeably differentA&O dynamics. The contribution of rotational states having different symmetry,weighted by nuclear-spin statistics, to the A&O dynamics is also studied.

A quantum-chemical perspective on the laser-induced alignment and orientation dynamics of the CH$_3$X (X = F, Cl, Br, I) molecules