Automatic generation of active coordinates for quantum dynamics calculations: application to the dynamics of benzene photochemistry

A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments

A quantum molecular similarity analysis of changes in molecular electron density caused by basis set flotation and electric field application

Quantum molecular similarity (QMS) techniques are used to assess the response of the electron density of various small molecules to application of a static, uniform electric field. Likewise, QMS is used to analyze the changes in electron density generated by the process of floating a basis set. The results obtained show an interrelation between the floating process, the optimum geometry, and the presence of an external field. Cases involving the Le Chatelier principle are discussed, and an insight on the changes of bond critical point properties, self-similarity values and density differences is performed

Electronic couplings and on-site energies for hole transfer in DNA: systematic quantum mechanical/molecular dynamic study

The electron hole transfer (HT) properties of DNA are substantially affected by thermal fluctuations of the π stack structure. Depending on the mutual position of neighboring nucleobases, electronic coupling V may change by several orders of magnitude. In the present paper, we report the results of systematic QM/molecular dynamic (MD) calculations of the electronic couplings and on-site energies for the hole transfer. Based on 15 ns MD trajectories for several DNA oligomers, we calculate the average coupling squares 〈 V2 〉 and the energies of basepair triplets X G+ Y and X A+ Y, where X, Y=G, A, T, and C. For each of the 32 systems, 15 000 conformations separated by 1 ps are considered. The three-state generalized Mulliken-Hush method is used to derive electronic couplings for HT between neighboring basepairs. The adiabatic energies and dipole moment matrix elements are computed within the INDO/S method. We compare the rms values of V with the couplings estimated for the idealized B -DNA structure and show that in several important cases the couplings calculated for the idealized B -DNA structure are considerably underestimated. The rms values for intrastrand couplings G-G, A-A, G-A, and A-G are found to be similar, ∼0.07 eV, while the interstrand couplings are quite different. The energies of hole states G+ and A+ in the stack depend on the nature of the neighboring pairs. The X G+ Y are by 0.5 eV more stable than X A+ Y. The thermal fluctuations of the DNA structure facilitate the HT process from guanine to adenine. The tabulated couplings and on-site energies can be used as reference parameters in theoretical and computational studies of HT processes in DNA

Quantum cavitation in liquid helium

Using a functional-integral approach, we have determined the temperature below which cavitation in liquid helium is driven by thermally assisted quantum tunneling. For both helium isotopes, we have obtained the crossover temperature in the whole range of allowed negative pressures. Our results are compatible with recent experimental results on 4He.

Quantum nonlocality in two three-level systems

Recently a new Bell inequality has been introduced by Collins et al. [Phys. Rev. Lett. 88, 040404 (2002)], which is strongly resistant to noise for maximally entangled states of two d-dimensional quantum systems. We prove that a larger violation, or equivalently a stronger resistance to noise, is found for a nonmaximally entangled state. It is shown that the resistance to noise is not a good measure of nonlocality and we introduce some other possible measures. The nonmaximally entangled state turns out to be more robust also for these alternative measures. From these results it follows that two von Neumann measurements per party may be not optimal for detecting nonlocality. For d=3,4, we point out some connections between this inequality and distillability. Indeed, we demonstrate that any state violating it, with the optimal von Neumann settings, is distillable.

Separability and distillability of multiparticle quantum systems

We present a family of 3-qubit states to which any arbitrary state can be depolarized. We fully classify those states with respect to their separability and distillability properties. This provides a sufficient condition for nonseparability and distillability for arbitrary states. We generalize our results to N-particle states.

Generalized Schmidt decomposition and classification of three-quantum-bit states

We prove for any pure three-quantum-bit state the existence of local bases which allow one to build a set of five orthogonal product states in terms of which the state can be written in a unique form. This leads to a canonical form which generalizes the two-quantum-bit Schmidt decomposition. It is uniquely characterized by the five entanglement parameters. It leads to a complete classification of the three-quantum-bit states. It shows that the right outcome of an adequate local measurement always erases all entanglement between the other two parties.

Optimal strategies for sending information through a quantum channel

Quantum states can be used to encode the information contained in a direction, i.e., in a unit vector. We present the best encoding procedure when the quantum state is made up of N spins (qubits). We find that the quality of this optimal procedure, which we quantify in terms of the fidelity, depends solely on the dimension of the encoding space. We also investigate the use of spatial rotations on a quantum state, which provide a natural and less demanding encoding. In this case we prove that the fidelity is directly related to the largest zeros of the Legendre and Jacobi polynomials. We also discuss our results in terms of the information gain.

Semiclassical coupled wave theory and its application to TE waves in one dimensional crystals

A semiclassical coupled-wave theory is developed for TE waves in one-dimensional periodic structures. The theory is used to calculate the bandwidths and reflection/transmission characteristics of such structures, as functions of the incident wave frequency. The results are in good agreement with exact numerical simulations for an arbitrary angle of incidence and for any achievable refractive index contrast on a period of the structure.

Hamilton Jacobi theory for constrained systems

We extend the HamiltonJacobi formulation to constrained dynamical systems. The discussion covers both the case of first-class constraints alone and that of first- and second-class constraints combined. The HamiltonDirac equations are recovered as characteristic of the system of partial differential equations satisfied by the HamiltonJacobi function.

Canonical transformations theory for presymplectic systems

We develop a theory of canonical transformations for presymplectic systems, reducing this concept to that of canonical transformations for regular coisotropic canonical systems. In this way we can also link these with the usual canonical transformations for the symplectic reduced phase space. Furthermore, the concept of a generating function arises in a natural way as well as that of gauge group.

Hamilton-Jacobi theory for constrained systems

We extend the HamiltonJacobi formulation to constrained dynamical systems. The discussion covers both the case of first-class constraints alone and that of first- and second-class constraints combined. The HamiltonDirac equations are recovered as characteristic of the system of partial differential equations satisfied by the HamiltonJacobi function.