Interactive Chemical Reactivity Exploration

Elucidating chemical reactivity in complex molecular assemblies of a few hundred atoms is, despite the remarkable progress in quantum chemistry, still a major challenge. Black-box search methods to find intermediates and transition-state structures might fail in such situations because of the high-dimensionality of the potential energy surface. Here, we propose the concept of interactive chemical reactivity exploration to effectively introduce the chemist's intuition into the search process. We employ a haptic pointer device with force-feedback to allow the operator the direct manipulation of structures in three dimensions along with simultaneous perception of the quantum mechanical response upon structure modification as forces. We elaborate on the details of how such an interactive exploration should proceed and which technical difficulties need to be overcome. All reactivity-exploration concepts developed for this purpose have been implemented in the Samson programming environment.Comment: 36 pages, 14 figure

Physical consequences of P≠\neqNP and the DMRG-annealing conjecture

Computational complexity theory contains a corpus of theorems and conjectures regarding the time a Turing machine will need to solve certain types of problems as a function of the input size. Nature {\em need not} be a Turing machine and, thus, these theorems do not apply directly to it. But {\em classical simulations} of physical processes are programs running on Turing machines and, as such, are subject to them. In this work, computational complexity theory is applied to classical simulations of systems performing an adiabatic quantum computation (AQC), based on an annealed extension of the density matrix renormalization group (DMRG). We conjecture that the computational time required for those classical simulations is controlled solely by the {\em maximal entanglement} found during the process. Thus, lower bounds on the growth of entanglement with the system size can be provided. In some cases, quantum phase transitions can be predicted to take place in certain inhomogeneous systems. Concretely, physical conclusions are drawn from the assumption that the complexity classes {\bf P} and {\bf NP} differ. As a by-product, an alternative measure of entanglement is proposed which, via Chebyshev's inequality, allows to establish strict bounds on the required computational time.Comment: Accepted for publication in JSTA