We report three-dimensional quantum mechanical calculations on the photodissociation dynamics of CH3I and CD3I on new ab initio potential energy surfaces. The improved potentials are obtained in the contracted spin−orbit configuration interaction framework by using a larger basis set and more spin-free configurations. The dynamical model includes the C−I stretch, C−H3 umbrella bend, and I−C−H3 bend and allows the overall rotation. The wave packet is propagated in the Chebyshev order domain. The absorption spectrum, product vibrational and rotational distributions, I* quantum yield, and state-resolved angular distributions are calculated for the parent states of |JMK〉 = |000〉 and |111〉, and compared with experiments. The new potential energy surfaces yield a much better agreement with the experimental absorption spectrum, thanks to small potential gradients in the Franck−Condon region. The calculated rovibrational distributions of the methyl fragment are also in good agreement with experimental data. It is shown that the overall rotation has significant effects on the methyl rotational and vibrational distributions as well as the I* yield.

State-to-state photodissociation dynamics of H(2)O in its B band has been investigated quantum mechanically on a new set of non-adiabatically coupled potential energy surfaces for the lowest two (1)A' states of H(2)O, which are developed at the internally contracted multi-reference configuration interaction level with the aug-cc-pVQZ basis set. Quantum dynamical calculations carried out using the Chebyshev propagator yield absorption spectra, product state distributions, branching ratios, and differential cross sections, which are in reasonably good agreement with the latest experimental results. Particular focus is placed here on the dependence of various dynamical observables on the photon energy. Detailed analyses of the dynamics have assigned the diffuse structure in absorption spectrum to short-time recurring dynamics near the HOH conical intersection. The non-adiabatic dissociation to the ground state OH product via the HOH conical intersection is facile, direct, fast, and produces rotationally hot OH(X̃) products. On the other hand, the adiabatic channel on the excited state leading to the OH(Ã) product is dominated by long-lived resonances, which depend sensitively on the potential energy surfaces.

A new global potential-energy surface for the ground electronic state of HO(2)(X(2)A(")) has been developed by three-dimensional cubic spline interpolation of more than 15 000 ab initio points, which were calculated at the multireference configuration-interaction level with Davidson correction using the augmented correlation-consistent polarized valence quadruple zeta basis set. Low-lying vibrational states were obtained in this new potential using the Lanczos method and assigned. The calculated vibrational frequencies are in much better agreement with the available experimental band origins than those obtained from a previous potential. In addition, rate constants for the H+O(2) <--> O + OH reactions were obtained using a wave-packet-based statistical model. Reasonably good agreement with experimental data was obtained. These results demonstrate the accuracy of the potential.

Three-dimensional potential energy surfaces for the two lowest singlet (Ã(1)B1 and B̃(1)A2) and two lowest triplet (ã(3)B1 and b̃(3)A2) states of SO2 have been determined at the Davidson corrected internally contracted multi-reference configuration interaction level with the augmented correlation-consistent polarized triple-zeta basis set (icMRCI+Q∕AVTZ). The non-adiabatically coupled singlet states, which are responsible for the complex Clements bands of the B band, are expressed in a 2 × 2 quasi-diabatic representation. The triplet state potential energy surfaces, which are responsible for the weak A band, were constructed in the adiabatic representation. The absorption spectrum spanning both the A and B bands, which is calculated with a three-state non-adiabatic coupled Hamiltonian, is in good agreement with experiment, thus validating the potential energy surfaces and their couplings.

We present accurate differential and integral cross sections for the H + O2 --> OH + O reaction obtained on a newly developed ab initio potential energy surface using time-independent and time-dependent quantum mechanical methods. The product angular distributions near the reaction threshold show pronounced forward and backward peaks, reflecting the complex-forming mechanism. However, the asymmetry of these peaks suggests certain nonstatistical behaviors, presumably due to some relatively short-lived resonances. The integral cross section increases monotonically with the collision energy above a reaction threshold.

Aspirin, one of the oldest and most common anti-inflammatory agents, has recently been shown to reduce cancer risks. The principal pharmacological effects of aspirin are known to arise from its covalent modification of cyclooxygenase-2 (COX-2) through acetylation of Ser530, but the detailed mechanism of its biochemical action and specificity remains to be elucidated. In this work, we have filled this gap by employing a state-of-the-art computational approach, Born–Oppenheimer molecular dynamics simulations with ab initio quantum mechanical/molecular mechanical potential and umbrella sampling. Our studies have characterized a substrate-assisted inhibition mechanism for aspirin acetylating COX: it proceeds in two successive stages with a metastable tetrahedral intermediate, in which the carboxyl group of aspirin serves as the general base. The computational results confirmed that aspirin would be 10–100 times more potent against COX-1 than against COX-2, and revealed that this inhibition specificity between the two COX isoforms can be attributed mainly to the difference in kinetics rate of the covalent inhibition reaction, not the aspirin-binding step. The structural origin of this differential inhibition of the COX enzymes by aspirin has also been elucidated.

Green fluorescent proteins (GFPs) are widely used as tools in biochemistry, cell biology, and molecular genetics due to their unusual optical spectroscopic characteristics. The spectrophotometric and fluorescence properties of GFPs are controlled by the protonation states and possibly cis-trans isomerization of the chromophore (p-hydroxybenzylideneimidazolinone). In this work, we have investigated electronic structures, liquid structures, and solvent shifts of the three possible protonated states (neutral, anionic, and zwitterionic) and their cis-trans isomerization of a model compound 4'-hydroxybenzylidene-2-methyl-imidazolin-5-one-3-acetate (HBMIA) in aqueous solutions. Our calculated results suggest that HBMIA could adopt both cis and trans conformations in a solution, and it exists in three different protonation states depending on the pH conditions. The absorption spectrum observed in neutral solution is thus assigned to the electronic excitations within the neutral form and the cis isomer of the zwitterionic form, while the absorption band at 425 nm in the basic solution is due to the excitations within the anionic form and the trans isomer of the zwitterionic form. Some technical problems related to the computation of electronic excitations within the HBMIA at the anionic state are also discussed.

We present accurate quantum calculations of the integral cross section and rate constant for the H + O2 --> OH + O combustion reaction on a recently developed ab initio potential energy surface using parallelized time-dependent and Chebyshev wavepacket methods. Partial wave contributions up to J = 70 were computed with full Coriolis coupling, which enabled us to obtain the initial state-specified integral cross sections up to 2.0 eV of the collision energy and thermal rate constants up to 3000 K. The integral cross sections show a large reaction threshold due to the quantum endothermicity of the reaction, and they monotonically increase with the collision energy. As a result, the temperature dependence of the rate constant is of the Arrhenius type. In addition, it was found that reactivity is enhanced by reactant vibrational excitation. The calculated thermal rate constant shows a significant improvement over that obtained on the DMBE IV potential, but it still underestimates the experimental consensus.