RESUMO
The influence of phosphorus substitution of nitrogen in heterocyclic compounds on the vibrational spectroscopy as well as frontier molecular orbitals are analyzed. Nicotine with two nitrogen atoms in its structure is taken as the sample system to be studied computationally. By replacing the nitrogen atom in one or both rings of this molecule with phosphorus, three nicotine derivatives are created. The vibrational circular dichroism and infrared spectra of these four molecules in their monomer state, as well as the assemblies up to trimers are determined. The aforementioned spectra are calculated using static quantum chemical calculations employing a cluster-weighted approach. The calculated gas phase spectra of nicotine are compared to their respective experimental spectra. It is observed that the nicotine derivatives with phosphorus in the methylpyrrolidine ring have considerably different gas phase and bulk phase vibrational circular dichroism spectra when compared to nicotine. The phosphorus substitution reduces the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital as well as altering the polarizability and reactivity of the investigated molecules.
RESUMO
Weighting methods applied to systems with many conformers have been broadly employed to calculate thermodynamic properties, structural characteristics, and populations. To better understand and test the sensitivity of conventional weighting methods, the conformational distributions of nicotine and its phosphorus-substituted derivatives are investigated. The weighting schemes used for this are all based on Boltzmann statistics. Classical Boltzmann factors based on the electronic energy and the Gibbs free energy are calculated at different quantum chemical levels of theory and compared to cluster weights obtained by the quantum cluster equilibrium method. Furthermore, the influence of the modified rigid-rotor-harmonic-oscillator (mRRHO) approximation on the cluster weights is investigated. The substitution of the nitrogen atom in the methylpyrrolidine ring by a phosphorus atom results in more monomer conformers and clusters being populated. The conformational distribution of the monomers remained stable at different levels of theory and weighting methods. However, going to dimers and trimers, we observe a significant influence of the level of theory, weighting method, and mRRHO cutoff on the populations of these clusters. We show that mRRHO cutoff values of 50 and 100 cm-1 yield similar results, which is why 50 cm-1 is recommended as a robust choice. Furthermore, we observe that the global minimum for ΔE0 and ΔG varies in a few cases and that the global minimum is not always the dominantly occupied structure.
