Ground- and Triplet Excited-State Properties Correlation: A Computational CASSCF/CASPT2 Approach Based on the Photodissociation of Allylsilanes

Abstract

Excited-state properties, although extremely useful, are hardly accessible. One indirect way would be to derive them from relationships to ground-state properties which are usually more readily available. Herewith, we present quantitative correlations between triplet excited-state (T₁) properties (bond dissociation energy, D₀(T₁), homolytic activation energy, E(a)(T₁), and rate constant, k(r)) and the ground-state bond dissociation energy (D₀), taking as an example the photodissociation of the C-Si bond of simple substituted allylsilanes CH₂=CHC(R¹R²)-SiH₃ (R¹ and R² = H, Me, and Et). By applying the complete-active-space self-consistent field CASSCF(6,6) and CASPT2(6,6) quantum chemical methodologies, we have found that the consecutive introduction of Me/Et groups has little effect on the geometry and energy of the T₁ state; however, it reduces the magnitudes of D₀, D₀(T₁) and E(a)(T₁). Moreover, these energetic parameters have been plotted giving good linear correlations: D₀(T₁) = α₁ + β₁ · D₀, E(a)(T₁) = α₂ + β₂ · D₀(T₁), and E(a)(T₁) = α₃ + β₃ · D₀ (α and β being constants), while k(r) correlates very well to E(a)(T₁). The key factor behind these useful correlations is the validity of the Evans-Polanyi-Semenov relation (second equation) and its extended form (third equation) applied for excited systems. Additionally, the unexpectedly high values obtained for E(a)(T₁) demonstrate a new application of the principle of nonperfect synchronization (PNS) in excited-state chemistry issues.