We proposed and implemented a combined molecular dynamics and coordinate driving (MD/CD) method for automatically searching multistep reaction pathways of chemical reactions. In this approach, the molecular dynamic (MD) method at the molecular mechanics (MM) or semiempirical quantum mechanical (QM) level is employed to explore the conformational space of the minimum structures, and the modified coordinate driving (CD) method is used to build reaction pathways for representative conformers. The MD/CD method is first applied to two model reactions (the Claisen rearrangement and the intermolecular aldol reaction). By comparing the obtained results with those of the existing methods, we found that the MD/CD method has a comparable performance in searching low-energy reaction pathways. Then, the MD/CD method is further applied to investigate two reactions: the electrocyclic reaction of benzocyclobutene-7-carboxaldehyde and the intramolecular Diels-Alder reaction of ketothioester with 11 effectively rotatable single bonds. For the first reaction, our results can correctly account for its torquoselectivity. For the second one, our method predicts eight reaction channels, leading to eight different stereo- and regioselective products. The MD/CD method is expected to become an efficient and cost-effective theoretical tool for automatically searching low-energy reaction pathways for relatively complex chemical reactions.

We propose an efficient general strategy for generating initial orbitals for generalized valence bond (GVB) calculations which makes routine black-box GVB calculations on large systems feasible. Two schemes are proposed, depending on whether the restricted Hartree−Fock (RHF) wave function is stable (scheme I) or not (scheme II). In both schemes, the first step is the construction of active occupied orbitals and active virtual orbitals. In scheme I, active occupied orbitals are composed of the valence orbitals (the inner core orbitals are excluded), and the active virtual orbitals are obtained from the original virtual space by requiring its maximum overlap with the virtual orbital space of the same system at a minimal basis set. In scheme II, active occupied orbitals and active virtual orbitals are obtained from the set of unrestricted natural orbitals (UNOs), which are transformed from two sets of unrestricted HF spatial orbitals. In the next step, the active occupied orbitals and active virtual ones are separately transformed to localized orbitals. Localized occupied and virtual orbital pairs are formed using the Kuhn−Munkres (KM) algorithm and are used as the initial guess for the GVB orbitals. The optimized GVB wave function is obtained using the second-order self-consistent-field algorithm in the GAMESS program. With this procedure, GVB energies have been obtained for the lowest singlet and triplet states of polyacenes (up to decacene with 96 pairs) and the singlet ground state of two di-copper−oxygen−ammonia complexes. We have also calculated the singlet−triplet gaps for some polyacenes and the relative energy between two di-copper−oxygen−ammonia complexes with the blockcorrelated second-order perturbation theory based on the GVB reference.

A block-correlated coupled cluster (BCCC) method based on the generalized valence bond (GVB) wave function (GVB-BCCC in short) is proposed and implemented at the ab initio level, which represents an attractive multireference electronic structure method for strongly correlated systems. The GVB-BCCC method is demonstrated to provide accurate descriptions for multiple bond breaking in small molecules, although the GVB reference function is qualitatively wrong for the studied processes. For a challenging prototype of strongly correlated systems, tridecane with all 12 single C-C bonds at various distances, our calculations have shown that the GVB-BCCC2b method can provide highly comparable results as the density matrix renormalization group method for potential energy surfaces along simultaneous dissociation of all C-C bonds.

The accurate multireference (MR) calculation of a strongly correlated chemical system usually relies on a correct preselection of a small number of active orbitals from numerous molecular orbitals. Currently, the active orbitals are generally determined by using a trial-and-error method. Such a preselection by chemical intuition and personal experience may be tedious or unreliable, especially for large complicated systems, and accordingly, the construction of active space becomes a bottleneck for large-scale MR calculations. In this work, we propose to automatically select the active orbitals according to the natural orbital occupation numbers by performing black box generalized valence bond calculations. We demonstrate the accuracy of this method through testing calculations of the ground states in various systems, ranging from bond dissociation of diatomic molecules (N2, C2, Cr2) to conjugated molecules (pentacene, hexacene, and heptacene) as well as a binuclear transition-metal complex [Mn2O2(H2O)2(terpy)2]3+ (terpy = 2,2′:6,2″-terpyridine) with active spaces up to (30e, 30o) and comparing with the complete active space self-consistent field (CASSCF), density matrix renormalization group (DMRG)-CASSCF references, and other recently proposed inexpensive strategies for constructing active spaces. The results indicate that our method is among the most successful ones within our comparison, providing high-quality initial active orbitals very close to the finally optimized (DMRG-)­CASSCF orbitals. The method proposed here is expected to greatly benefit the practical implementation of large active space ground-state MR calculations, for example, large-scale DMRG calculations.

A novel compound 4-amino-5-mercapto-1,2,4-triazole was first synthesized, and its selective adsorption mechanism on the surface of chalcopyrite was comprehensively investigated using UV-vis spectra, zeta-potential, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy measurements (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and first principles calculations. The experimental and computational results consistently demonstrated that AMT would chemisorb onto the chalcopyrite surface by the formation of a five-membered chelate ring. The first principles periodic calculations further indicated that AMT would prefer to adsorb onto Cu rather than Fe due to the more negative adsorption energy of AMT on Cu in the chalcopyrite (001) surface, which was further confirmed by the coordination reaction energies of AMT-Cu and AMT-Fe based on the simplified cluster models at a higher accuracy level (UB3LYP/Def2-TZVP). The bench-scale results indicated that the selective index improved significantly when using AMT as a chalcopyrite depressant in Cu-Mo flotation separation.