Toward spin-orbit coupled diabatic potential energy surfaces for methyl iodide using effective relativistic coupling by asymptotic representation.

The theoretical treatment of state-state interactions and the development of coupled multidimensional potential energy surfaces (PESs) is of fundamental importance for the theoretical investigation of nonadiabatic processes. Usually, only derivative or vibronic coupling is considered, but the presence of heavy atoms in a system can render spin-orbit (SO) coupling important as well. In the present study, we apply a new method recently developed by us (J. Chem. Phys. 2012, 136, 034103, and J. Chem. Phys. 2012, 137, 064101) to generate SO coupled diabatic PESs along the C-I dissociation coordinate for methyl iodide (CH3I). This is the first and mandatory step toward the development of fully coupled full-dimensional PESs to describe the multistate photodynamics of this benchmark system. The method we use here is based on the diabatic asymptotic representation of the molecular fine structure states and an effective relativistic coupling operator. It therefore is called effective relativistic coupling by asymptotic representation (ERCAR). This approach allows the efficient and accurate generation of fully coupled PESs including derivative and SO coupling based on high-level ab initio calculations. In this study we develop a specific ERCAR model for CH3I that so far accounts only for the C-I bond cleavage. Details of the diabatization and the accuracy of the results are investigated in comparison to reference ab initio calculations and experiments. The energies of the adiabatic fine structure states are reproduced in excellent agreement with ab initio SO-CI data. The model is also compared to available literature data, and its performance is evaluated critically. This shows that the new method is very promising for the construction of fully coupled full-dimensional PESs for CH3I to be used in future quantum dynamics studies.

Spin-orbit coupled potential energy surfaces and properties using effective relativistic coupling by asymptotic representation.

A new method has been reported recently [H. Ndome, R. Welsch, and W. Eisfeld, J. Chem. Phys. 136, 034103 (2012)] that allows the efficient generation of fully coupled potential energy surfaces (PESs) including derivative and spin-orbit (SO) coupling. The method is based on the diabatic asymptotic representation of the molecular fine structure states and an effective relativistic coupling operator and therefore is called effective relativistic coupling by asymptotic representation (ERCAR). The resulting diabatic spin-orbit coupling matrix is constant and the geometry dependence of the coupling between the eigenstates is accounted for by the diabatization. This approach allows to generate an analytical model for the fully coupled PESs without performing any ab initio SO calculations (except perhaps for the atoms) and thus is very efficient. In the present work, we study the performance of this new method for the example of hydrogen iodide as a well-established test case. Details of the diabatization and the accuracy of the results are investigated in comparison to reference ab initio calculations. The energies of the adiabatic fine structure states are reproduced in excellent agreement with reference ab initio data. It is shown that the accuracy of the ERCAR approach mainly depends on the quality of the underlying ab initio data. This is also the case for dissociation and vibrational level energies, which are influenced by the SO coupling. A method is presented how one-electron operators and the corresponding properties can be evaluated in the framework of the ERCAR approach. This allows the computation of dipole and transition moments of the fine structure states in good agreement with ab initio data. The new method is shown to be very promising for the construction of fully coupled PESs for more complex polyatomic systems to be used in quantum dynamics studies.

A new method to generate spin-orbit coupled potential energy surfaces: effective relativistic coupling by asymptotic representation.

A new method has been developed to generate fully coupled potential energy surfaces including derivative and spin-orbit coupling. The method is based on an asymptotic (atomic) representation of the molecular fine structure states and a corresponding diabatization. The effective relativistic coupling is described by a constant spin-orbit coupling matrix and the geometry dependence of the coupling is accounted for by the diabatization. This approach is very efficient, particularly for certain systems containing a very heavy atom, and yields consistent results throughout nuclear configuration space. A first application to a diatomic system is presented as proof of principle and is compared to accurate ab initio calculations. However, the method is widely applicable to general polyatomic systems in full dimensionality, containing several relativistic atoms and treating higher order relativistic couplings as well.

UV-visible absorption spectra of small platinum carbonyl complexes and particles: a density functional theory study.

We investigate the influence of a carbonyl coating on the UV-visible absorption of platinum complexes and particles with the TDDFT method. We first investigate the Chini clusters [Pt(3)(CO)(6)](n)(2-), n = 1-4, for which the absorption spectra are known. We show that PBE is realistic but displays convergence issues and that B3LYP overestimates intertriangle distances and absorption intensities. We discuss the structure of the spectra and the parallel vs perpendicular character of the transition dipole with respect to the stacking axis. We then investigate the spectra of model carbonylated platinum particles: [Pt(13)(CO)(12)](2-) (with only terminal carbonyls) and [Pt(13)(CO)(24)](2-) (with only bridging carbonyls). B3LYP proves much more realistic than in the case of Chini clusters. The influence of the morphology of the platinum particle and of the carbonyl coating on the absorption spectra is discussed. The results suggest an interpretation of a spectrum, recorded in a recent synthesis.