No abstract

We present a full analysis of the magnitude and orientation of the diabatic transition matrix element of a general vectorial physical observable during the adiabatic-to-diabatic transformation. The diabatic transition is a function of the adiabatic-to-diabatic transformation angle and the two basic vectors of the adiabatic states, which are the off-diagonal matrix element and the difference between the two diagonal matrix elements. To the best of our knowledge, this is the first time that the transformation has been accomplished in a more general two-dimensional scale for a vectorial physical observable. All possible extreme values of a diabatic transition are deduced for systems with different features. By using an approximate diabatic transition dipole, the pilot implementation of the analysis produces an electronic coupling curve nearly identical to that obtained by the generalized Mulliken–Hush method for the testing molecule. Evidently, this complete analysis of a diabatic transition will be very useful in determining the adiabatic-to-diabatic transformation angle by using a physical observable and can also be used to evaluate the quality of various approximations for constructing the diabatic states.

A novel adiabatic-to-diabatic (ATD) transformation strategy, namely, the extended Mulliken–Hush (XMH) method, is proposed to evaluate diabatic properties including electronic couplings, potential energy surfaces, and their crossings. The XMH method is developed by adopting our recently proposed ATD transformation formula of a general vectorial physical observable, in which a useful ATD transformation is further determined by using an auxiliary dipole between localized frontier orbitals as a simple approximation of the diabatic transition dipole. The XMH method is simple and practical that provides a flexible way to construct diabatic states. To some extent, it can be regarded as an extension of the generalized Mulliken–Hush (GMH) method since the latter takes a stronger approximation, in which the diabatic transition dipole is assumed to be vanishing. Test calculations on the HeH2 + system show that the electronic couplings predicted by the XMH method are closer to the ones calculated by the valence bond block-diagonalization approach than the GMH ones since the XMH method takes into account both the magnitude and direction of the diabatic transition dipole, which is consistent with the properties of this molecule. In the study of electron transfer in the two kinds of donor-bridge-acceptor systems, the XMH method maintains the simplicity of the GMH method and gives reasonable results even when the latter fails, wherein the diabatic transition dipole is nearly perpendicular to the difference of the initial and final adiabatic dipoles. More importantly, the XMH method can be easily combined with high-level electronic structure methods, in which the properties of the ground and excited states may be more accurately calculated, and hence, one may expect that further development of the XMH method would result in a general computational model for studying electron transfer reactions.

The paper combines the valence bond block diabatization approach (VBBDA) with the idea of orbital breathing. With highly compact wave functions, the breathing orbital valence bond (BOVB) method is applied to investigate several atomic and molecular properties including the electron affinity of F, the adiabatic and diabatic potential energy curves and the dipole moment curves of the two lowest-lying 1Σ+ states, the electronic coupling curve and the crossing distance of the two diabatic states, and the spectroscopic constants of the ground states for LiF. The configuration selection scheme proposed in this work is quite general, requiring only the selection of several de-excitation and excitation orbitals in a sense like the restricted active space self-consistent field method. Practically, this is also the first time that BOVB results are extrapolated to complete basis set limit. Armed with the chemical intuition provided by VB theory, the classic but challenging covalent-ionic interaction in the title molecule is not only conceptually interpreted but is also accurately computed.