Vibrational Averaging Of The Isotropic Hyperfine Coupling Constants For The Methyl Radical

Abstract

Electronic contributions to molecular properties are often considered as the major factor and usually reported in the literature without ro-vibrational corrections. However, there are many cases where the nuclear motion contributions are significant and even larger than the electronic contribution. In order to obtain accurate theoretical predictions, nuclear motion effects on molecular properties need to be taken into account. The computed isotropic hyperfine coupling constants for the nonvibrating methyl radical CH$_3$ are far from the experimental values. For CH$_3$, we have calculated the vibrational-state-dependence of the isotropic hyperfine coupling constant in the electronic ground state. The vibrational wavefunctions used in the averaging procedure were obtained variationally with the TROVE program. Analytical representations for the potential energy surfaces and the hyperfine coupling constant surfaces are obtained in least-squares fitting procedures. Thermal averaging has been carried out for molecules in thermal equilibrium, i.e., with Boltzmann-distributed populations. The calculation methods and the results will be discussed in detail.