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Quantum dynamics simulations are an important tool to evaluate molecular behaviour including the, often key, quantum nature of the system. In this paper we present an algorithm that is able to simulate the time evolution of a molecule after photo-excitation into a manifold of states. The direct dynamics variational multi-configurational Gaussian (DD-vMCG) method circumvents the computational bottleneck problems of traditional grid-based methods by computing the potential energy functions on-the-fly, i.e. only where required. Unlike other commonly used direct dynamics methods, DD-vMCG is fully quantum mechanical. Here, the method is combined with a novel on-the-fly diabatisation scheme to simulate the short-time dynamics of the key molecule formamide and its acid analogue formimidic acid. This is a challenging test system due to the nature and large number of excited states, and eight coupled states are included in the calculations. It is shown that the method is able to provide unbiased information on the product channels open after excitation at different energies and demonstrates the potential to be a practical scheme, limited mainly by the quality of the quantum chemistry used to describe the excited states.

The Stark effect is produced when a static field alters molecular states. When the field applied is time dependent, the process is known as the dynamic Stark effect. Of particular interest for the control of molecular dynamics is the Non-Resonant Dynamic Stark Effect (NRDSE), in which the time dependent field is unable to effect a one-photon excitation. The intermediate strength laser pulse instead shapes the potential energy surfaces (PES) and so guides the evolution of the system. A prototype control scheme uses the NRDSE to change the topography of PES in regions where they intersect, thus providing control over photochemistry. Following earlier experimental work, in this paper we study the NRDSE on a new 3 state model of the IBr molecule to gain insight into the mechanism of control at the avoided crossing that governs the branching ratio of the photodissociation.

In a recent paper (G. Worth, P. Hunt and M. Robb, J. Phys. Chem. A, 2003, 107, 621), we used surface hopping direct dynamics calculations to study the molecular dynamics of the butatriene radical cation in the X/A manifold, which is coupled by a conical intersection. Here, we present the first direct dynamics calculations using a novel algorithm, again using this ideal test system. The algorithm, which is based on the powerful multi-configuration time-dependent Hartree (MCTDH) wavepacket propagation method, uses a variational basis of coupled frozen Gaussian functions that optimally represent the evolving nuclear wavepacket at all times. Each Gaussian function follows a "quantum trajectory", along which the potential surface is evaluated by quantum chemistry calculations. As far fewer Gaussian functions are needed than classical trajectories in a semi-classical method, the number of quantum chemical calculations is drastically reduced. A crucial point in direct dynamics. To validate the method, initial calculations have been made using an analytic model Hamiltonian, where it is shown to reproduce the main features of the state population transfer with 8-16 basis functions per state. Coupled to the GAUSSIAN quantum chemistry program, the method is then shown to provide a feasible direct dynamics algorithm for the description of this non-adiabatic process.